Polymers functionalized with nitrile compounds containing a protected amino group

ABSTRACT

A method for preparing a functionalized polymer, the method comprising the steps of: (i) polymerizing monomer with an anionic initiator to form a reactive polymer; and (ii) reacting the reactive polymer with a nitrile compound containing a protected amino group, where the protected amino group is directly attached to a moiety selected from the group consisting of acyclic moieties, heterocyclic moieties, and non-aromatic cyclic moieties.

This application claims the benefit of U.S. Provisional Application Ser.No. 61/297,637, filed on Jan. 22, 2010, which is incorporated herein byreference.

FIELD OF THE INVENTION

One or more embodiments of the present invention relate tofunctionalized polymers and methods for their manufacture.

BACKGROUND OF THE INVENTION

In the art of manufacturing tires, it is desirable to employ rubbervulcanizates that demonstrate reduced hysteresis, i.e., less loss ofmechanical energy to heat. For example, rubber vulcanizates that showreduced hysteresis are advantageously employed in tire components, suchas sidewalls and treads, to yield tires having desirably low rollingresistance. The hysteresis of a rubber vulcanizate is often attributedto the free polymer chain ends within the crosslinked rubber network, aswell as the dissociation of filler agglomerates.

Functionalized polymers have been employed to reduce the hysteresis ofrubber vulcanizates. The functional group of the functionalized polymermay reduce the number of free polymer chain ends via interaction withfiller particles. Also, the functional group may reduce filleragglomeration. Nevertheless, whether a particular functional groupimparted to a polymer can reduce hysteresis is often unpredictable.

Functionalized polymers may be prepared by post-polymerization treatmentof reactive polymers with certain functionalizing agents. However,whether a reactive polymer can be functionalized by treatment with aparticular functionalizing agent can be unpredictable. For example,functionalizing agents that work for one type of polymer do notnecessarily work for another type of polymer, and vice versa.

Anionic initiators are known to be useful for the polymerization ofconjugated diene monomers to form polydienes having a combination of1,2-, cis-1,4- and trans-1,4-linkages. Anionic initiators are alsouseful for the copolymerization of conjugated diene monomers withvinyl-substituted aromatic compounds. The polymers prepared with anionicinitiators may display living characteristics in that, upon completionof the polymerization, the polymer chains possess living ends that arecapable of reacting with additional monomers for further chain growth orreacting with certain functionalizing agents to give functionalizedpolymers.

Because functionalized polymers are advantageous, especially in themanufacture of tires, there exists a need to develop new functionalizedpolymers that give reduced hysteresis.

SUMMARY OF THE INVENTION

Embodiments of the present invention provide a method for preparing afunctionalized polymer, the method comprising the steps of: (i)polymerizing monomer with an anionic initiator to form a reactivepolymer; and (ii) reacting the reactive polymer with a nitrile compoundcontaining a protected amino group, where the protected amino group isdirectly attached to a moiety selected from the group consisting ofacyclic moieties, heterocyclic moieties, and non-aromatic cyclicmoieties.

Embodiments of the present invention further provide a method forpreparing a functionalized polymer, the method comprising the steps of:(i) polymerizing monomer with an anionic initiator to form a reactivepolymer; and (ii) reacting the reactive polymer with a nitrile compoundcontaining a protected amino group defined by the formula I:

where R¹ is a divalent organic group, and R² and R³ are eachindependently a monovalent organic group or a hydrolyzable group, or R²and R³ join to form a divalent organic group, with the proviso that R¹is an acyclic divalent organic group, a heterocyclic divalent organicgroup, a non-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theprotected amino group is not directly attached to the aromatic ring.

Embodiments of the present invention further provide a functionalizedpolymer containing a protected amino group, the functionalized polymerbeing defined by the formula VII:

where π is a polymer chain of a polydiene or a copolymer of conjugateddiene and co-monomer having a medium or low cis-1,4-linkage content, R¹is a divalent organic group, and R² and R³ are each independently amonovalent organic group or a hydrolyzable group, or R² and R³ join toform a divalent organic group, with the proviso that R¹ is an acyclicdivalent organic group, a heterocyclic divalent organic group, anon-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theprotected amino group is not directly attached to the aromatic ring.

Embodiments of the present invention further provide a functionalizedpolymer containing an amino group, the functionalized polymer beingdefined by the formula VIII:

where π is a polymer chain of a polydiene or a copolymer of conjugateddiene and co-monomer having a medium or low cis-1,4-linkage content, R¹is a divalent organic group, and R¹² and R¹³ are each independently amonovalent organic group or a hydrogen atom, or R¹² and R¹³ join to forma divalent organic group, with the proviso that R¹ is an acyclicdivalent organic group, a heterocyclic divalent organic group, anon-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theamino group is not directly attached to the aromatic ring

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical plot of hysteresis loss (tan δ) versus Mooneyviscosity (ML 1+4 at 130° C.) for vulcanizates prepared fromfunctionalized poly(styrene-co-butadiene) prepared according to one ormore embodiments of the present invention as compared to vulcanizateprepared from unfunctionalized poly(styrene-co-butadiene).

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

According to one or more embodiments of the present invention, areactive polymer is prepared by anionically polymerizing conjugateddiene monomer and optionally monomer copolymerizable therewith, and thisreactive polymer is then functionalized by reaction with a nitrilecompound containing a protected amino group. The resultantfunctionalized polymers can be used in the manufacture of tirecomponents. In one or more embodiments, the resultant functionalizedpolymers provide tire components that exhibit advantageously lowhysteresis.

Examples of conjugated diene monomer include 1,3-butadiene, isoprene,1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, and 2,4-hexadiene. Mixtures of two or moreconjugated dienes may also be utilized in copolymerization.

Examples of monomer copolymerizable with conjugated diene monomerinclude vinyl-substituted aromatic compounds such as styrene,p-methylstyrene, α-methylstyrene, and vinylnaphthalene.

In accordance with the present invention, a reactive polymer is preparedby anionic polymerization, wherein monomer is polymerized by using ananionic initiator. The key mechanistic features of anionicpolymerization have been described in books (e.g., Hsieh, H. L.; Quirk,R. P. Anionic Polymerization: Principles and Practical Applications;Marcel Dekker: New York, 1996) and review articles (e.g.,Hadjichristidis, N.; Pitsikalis, M.; Pispas, S.; Iatrou, H.; Chem. Rev.2001, 101(12), 3747-3792). Anionic initiators may advantageously produceliving polymers that, prior to quenching, are capable of reacting withadditional monomers for further chain growth or reacting with certainfunctionalizing agents to give functionalized polymers.

The practice of this invention is not limited by the selection of anyparticular anionic initiators. In one or more embodiments, the anionicinitiator employed is a functional initiator that imparts a functionalgroup at the head of the polymer chain (i.e., the location from whichthe polymer chain is started). In particular embodiments, the functionalgroup includes one or more heteroatoms (e.g., nitrogen, oxygen, boron,silicon, sulfur, tin, and phosphorus atoms) or heterocyclic groups. Incertain embodiments, the functional group reduces the 50° C. hysteresisloss of carbon-black filled vulcanizates prepared from polymerscontaining the functional group as compared to similar carbon-blackfilled vulcanizates prepared from polymer that does not include thefunctional group.

Exemplary anionic initiators include organolithium compounds. In one ormore embodiments, organolithium compounds may include heteroatoms. Inthese or other embodiments, organolithium compounds may include one ormore heterocyclic groups. Types of organolithium compounds includealkyllithium, aryllithium compounds, and cycloalkyllithium compounds.Specific examples of organolithium compounds include ethyllithium,n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium,t-butyllithium, n-amyllithium, isoamyllithium, and phenyllithium.

In particular embodiments, the organolithium compounds include a cyclicamine-containing compound such as lithiohexamethyleneimine. These andrelated useful initiators are disclosed in the U.S. Pat. Nos. 5,332,810,5,329,005, 5,578,542, 5,393,721, 5,698,646, 5,491,230, 5,521,309,5,496,940, 5,574,109, and 5,786,441, which are incorporated herein byreference. In other embodiments, the organolithium compounds includelithiated alkylthioacetals such as 2-lithio-2-methyl-1,3-dithiane. Theseand related useful initiators are disclosed in U.S. Publ. Nos.2006/0030657, 2006/0264590, and 2006/0264589, which are incorporatedherein by reference. In still other embodiments, the organolithiumcompounds include alkoxysilyl-containing initiators, such as lithiatedt-butyldimethylpropoxysilane. These and related useful initiators aredisclosed in U.S. Publ. No. 2006/0241241, which is incorporated hereinby reference.

Other anionic initiators include organosodium compounds such asphenylsodium and 2,4,6-trimethylphenylsodium. Also contemplated arethose anionic initiators that give rise to di-living polymers, whereinboth ends of a polymer chain are living. Examples of such initiatorsinclude dilithio initiators such as those prepared by reacting1,3-diisopropenylbenzene with sec-butyllithium. These and relateddifunctional initiators are disclosed in U.S. Pat. No. 3,652,516, whichis incorporated herein by reference. Radical anionic initiators may alsobe employed, including those described in U.S. Pat. No. 5,552,483, whichis incorporated herein by reference.

In one or more embodiments, the anionic initiator employed istrialkyltinlithium compound such as tri-n-butyltinlithium. These andrelated useful initiators are disclosed in U.S. Pat. Nos. 3,426,006 and5,268,439, which are incorporated herein by reference.

When elastomeric copolymers containing conjugated diene monomers andvinyl-substituted aromatic monomers are prepared by anionicpolymerization, the conjugated diene monomers and vinyl-substitutedaromatic monomers may be used at a weight ratio of 95:5 to 50:50, or inother embodiments, 90:10 to 65:35. In order to promote the randomizationof comonomers in copolymerization and to control the microstructure(such as 1,2-linkage of conjugated diene monomer) of the polymer, arandomizer, which is typically a polar coordinator, may be employedalong with the anionic initiator.

Compounds useful as randomizers include those having an oxygen ornitrogen heteroatom and a non-bonded pair of electrons. Exemplary typesof randomizers include linear and cyclic oligomeric oxolanyl alkanes;dialkyl ethers of mono and oligo alkylene glycols (also known as glymeethers); crown ethers; tertiary amines; linear THF oligomers; alkalimetal alkoxides; and alkali metal sulfonates. Linear and cyclicoligomeric oxolanyl alkanes are described in U.S. Pat. No. 4,429,091,which is incorporated herein by reference. Specific examples ofrandomizers include 2,2-bis(2′-tetrahydrofuryl)propane,1,2-dimethoxyethane, N,N,N′,N′-tetramethylethylenediamine (TMEDA),tetrahydrofuran (THF), 1,2-dipiperidylethane, dipiperidylmethane,hexamethylphosphoramide, N,N′-dimethylpiperazine, diazabicyclooctane,dimethyl ether, diethyl ether, tri-n-butylamine, potassium t-amylate,potassium 4-dodecylsulfonate, and mixtures thereof.

The amount of randomizer to be employed may depend on various factorssuch as the desired microstructure of the polymer, the ratio of monomerto comonomer, the polymerization temperature, as well as the nature ofthe specific randomizer and initiator employed. In one or moreembodiments, the amount of randomizer employed may range between 0.05and 100 moles per mole of the anionic initiator.

The anionic initiator and the randomizer can be introduced to thepolymerization system by various methods. In one or more embodiments,the anionic initiator and the randomizer may be added separately to themonomer to be polymerized in either a stepwise or simultaneous manner.In other embodiments, the anionic initiator and the randomizer may bepre-mixed outside the polymerization system either in the absence of anymonomer or in the presence of a small amount of monomer, and theresulting mixture may be aged, if desired, and then added to the monomerthat is to be polymerized.

In one or more embodiments, regardless of what type of anionic initiatoris used to prepare the reactive polymer, a solvent may be employed as acarrier to either dissolve or suspend the initiator in order tofacilitate the delivery of the initiator to the polymerization system.In other embodiments, monomer can be used as the carrier. In yet otherembodiments, the initiator can be used in their neat state without anysolvent.

In one or more embodiments, suitable solvents include those organiccompounds that will not undergo polymerization or incorporation intopropagating polymer chains during the polymerization of monomer in thepresence of the initiator. In one or more embodiments, these organicspecies are liquid at ambient temperature and pressure. In one or moreembodiments, these organic solvents are inert to the initiator.Exemplary organic solvents include hydrocarbons with a low or relativelylow boiling point such as aromatic hydrocarbons, aliphatic hydrocarbons,and cycloaliphatic hydrocarbons. Non-limiting examples of aromatichydrocarbons include benzene, toluene, xylenes, ethylbenzene,diethylbenzene, and mesitylene. Non-limiting examples of aliphatichydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane,n-decane, isopentane, isohexanes, isopentanes, isooctanes,2,2-dimethylbutane, petroleum ether, kerosene, and petroleum spirits.And, non-limiting examples of cycloaliphatic hydrocarbons includecyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane.Mixtures of the above hydrocarbons may also be used. As is known in theart, aliphatic and cycloaliphatic hydrocarbons may be desirably employedfor environmental reasons. The low-boiling hydrocarbon solvents aretypically separated from the polymer upon completion of thepolymerization.

Other examples of organic solvents include high-boiling hydrocarbons ofhigh molecular weights, including hydrocarbon oils that are commonlyused to oil-extend polymers. Examples of these oils include paraffinicoils, aromatic oils, naphthenic oils, vegetable oils other than castoroils, and low PCA oils including MES, TDAE, SRAE, heavy naphthenic oils.Since these hydrocarbons are non-volatile, they typically do not requireseparation and remain incorporated in the polymer.

The production of the reactive polymer according to this invention canbe accomplished by polymerizing conjugated diene monomer, optionallytogether with monomer copolymerizable with conjugated diene monomer, inthe presence of a catalytically effective amount of an anionicinitiator. The introduction of the initiator, the conjugated dienemonomer, optionally the comonomer, and any solvent, if employed, forms apolymerization mixture in which the reactive polymer is formed. Theamount of the initiator to be employed may depend on the interplay ofvarious factors such as the type of initiator employed, the purity ofthe ingredients, the polymerization temperature, the polymerization rateand conversion desired, the molecular weight desired, and many otherfactors. Accordingly, a specific initiator amount cannot be definitivelyset forth except to say that catalytically effective amounts of theinitiator may be used.

In one or more embodiments, the initiator loading (e.g., an alkyllithiumcompound) may be varied from about 0.05 to about 100 mmol, in otherembodiments from about 0.1 to about 50 mmol, and in still otherembodiments from about 0.2 to about 5 mmol per 100 gram of monomer.

In one or more embodiments, the polymerization may be carried out in apolymerization system that includes a substantial amount of solvent. Inone embodiment, a solution polymerization system may be employed inwhich both the monomer to be polymerized and the polymer formed aresoluble in the solvent. In another embodiment, a precipitationpolymerization system may be employed by choosing a solvent in which thepolymer formed is insoluble. In both cases, an amount of solvent inaddition to the amount of solvent that may be used in preparing theinitiator is usually added to the polymerization system. The additionalsolvent may be the same as or different from the solvent used inpreparing the initiator. Exemplary solvents have been set forth above.In one or more embodiments, the solvent content of the polymerizationmixture may be more than 20% by weight, in other embodiments more than50% by weight, and in still other embodiments more than 80% by weightbased on the total weight of the polymerization mixture.

In other embodiments, the polymerization system employed may begenerally considered a bulk polymerization system that includessubstantially no solvent or a minimal amount of solvent. Those skilledin the art will appreciate the benefits of bulk polymerization processes(i.e., processes where monomer acts as the solvent), and therefore thepolymerization system includes less solvent than will deleteriouslyimpact the benefits sought by conducting bulk polymerization. In one ormore embodiments, the solvent content of the polymerization mixture maybe less than about 20% by weight, in other embodiments less than about10% by weight, and in still other embodiments less than about 5% byweight based on the total weight of the polymerization mixture. Inanother embodiment, the polymerization mixture contains no solventsother than those that are inherent to the raw materials employed. Instill another embodiment, the polymerization mixture is substantiallydevoid of solvent, which refers to the absence of that amount of solventthat would otherwise have an appreciable impact on the polymerizationprocess. Polymerization systems that are substantially devoid of solventmay be referred to as including substantially no solvent. In particularembodiments, the polymerization mixture is devoid of solvent.

The polymerization may be conducted in any conventional polymerizationvessels known in the art. In one or more embodiments, solutionpolymerization can be conducted in a conventional stirred-tank reactor.In other embodiments, bulk polymerization can be conducted in aconventional stirred-tank reactor, especially if the monomer conversionis less than about 60%. In still other embodiments, especially where themonomer conversion in a bulk polymerization process is higher than about60%, which typically results in a highly viscous cement, the bulkpolymerization may be conducted in an elongated reactor in which theviscous cement under polymerization is driven to move by piston, orsubstantially by piston. For example, extruders in which the cement ispushed along by a self-cleaning single-screw or double-screw agitatorare suitable for this purpose. Examples of useful bulk polymerizationprocesses are disclosed in U.S. Pat. No. 7,351,776, which isincorporated herein by reference.

In one or more embodiments, all of the ingredients used for thepolymerization can be combined within a single vessel (e.g., aconventional stirred-tank reactor), and all steps of the polymerizationprocess can be conducted within this vessel. In other embodiments, twoor more of the ingredients can be pre-combined in one vessel and thentransferred to another vessel where the polymerization of monomer (or atleast a major portion thereof) may be conducted.

The polymerization can be carried out as a batch process, a continuousprocess, or a semi-continuous process. In the semi-continuous process,the monomer is intermittently charged as needed to replace that monomeralready polymerized. In one or more embodiments, the conditions underwhich the polymerization proceeds may be controlled to maintain thetemperature of the polymerization mixture within a range from about −10°C. to about 200° C., in other embodiments from about 0° C. to about 150°C., and in other embodiments from about 20° C. to about 100° C. In oneor more embodiments, the heat of polymerization may be removed byexternal cooling by a thermally controlled reactor jacket, internalcooling by evaporation and condensation of the monomer through the useof a reflux condenser connected to the reactor, or a combination of thetwo methods. Also, the polymerization conditions may be controlled toconduct the polymerization under a pressure of from about 0.1 atmosphereto about 50 atmospheres, in other embodiments from about 0.5 atmosphereto about 20 atmosphere, and in other embodiments from about 1 atmosphereto about 10 atmospheres. In one or more embodiments, the pressures atwhich the polymerization may be carried out include those that ensurethat the majority of the monomer is in the liquid phase. In these orother embodiments, the polymerization mixture may be maintained underanaerobic conditions.

Some or all of the polymer chains in the resulting reactive polymer maypossess reactive chain ends before the polymerization mixture isquenched. As noted above, the reactive polymer prepared with an anionicinitiator (e.g., an alkyllithium initiator) may be referred to as aliving polymer. In one or more embodiments, a polymerization mixtureincluding the reactive polymer may be referred to as an activepolymerization mixture. The percentage of polymer chains possessing areactive end depends on various factors such as the type of initiator,the type of monomer, the purity of the ingredients, the polymerizationtemperature, the monomer conversion, and many other factors. In one ormore embodiments, at least about 20% of the polymer chains possess areactive end, in other embodiments at least about 50% of the polymerchains possess a reactive end, and in still other embodiments at leastabout 80% of the polymer chains possess a reactive end. In any event,the reactive polymer, or more specifically the reactive chain end of thepolymer, can be reacted with a nitrile compound containing a protectedamino group to form the functionalized polymer of this invention.

In one or more embodiments, nitrile compounds containing a protectedamino group include those compounds that contain one or more protectedamino groups and one or more cyano groups. For purposes of thisspecification, and for ease of explanation, the nitrile compoundscontaining a protected amino group may be simply referred to as thenitrile compounds.

In one or more embodiments, a cyano group, which may also be referred toas a nitrile group, may be defined by the formula —C≡N.

In one or more embodiments, protected amino groups include those aminogroups that are formed or derived by replacing the two hydrogen atoms ofthe parent amino group (i.e. —NH₂) with other substituents such ashydrocarbyl or silyl groups. In one or more embodiments, a protectedamino group may be defined by the formula —NR₂, where each R group isindependently a hydrocarbyl group or a silyl group. Where the protectedamino group includes a silyl group and a hydrocarbyl group, the groupmay be referred to as a monosilylated amino group. Where the protectedamino group includes two silyl groups, the group may be referred to as adisilylated amino group. Where the protected amino group includes twohydrocarbyl groups, the group may be referred to as a dihydrocarbylaminogroup.

Exemplary types of protected amino groups include, but are not limitedto, bis(trihydrocarbylsilyl)amino, bis(dihydrocarbylhydrosilyl)amino,1-aza-disila-1-cyclohydrocarbyl,(trihydrocarbylsilyl)(hydrocarbyl)amino,(dihydrocarbylhydrosilyl)(hydrocarbyl)amino,1-aza-2-sila-1-cyclohydrocarbyl, dihydrocarbylamino, and1-aza-1-cyclohydrocarbyl groups.

Specific examples of bis(trihydrocarbylsilyl)amino groups include, butare not limited to, bis(trimethylsilyl)amino, bis(triethylsilyl)amino,bis(triisopropylsilyl)amino, bis(tri-n-propylsilyl)amino,bis(triisobutylsilyl)amino, bis(tri-t-butylsilyl)amino, andbis(triphenylsilyl)amino groups.

Specific examples of bis(dihydrocarbylhydrosilyl)amino groups include,but are not limited to, bis(dimethylhydrosilyl)amino,bis(diethylhydrosilyl)amino, bis(diisopropylhydrosilyl)amino,bis(di-n-propylhydrosilyl)amino, bis(diisobutylhydrosilyl)amino,bis(di-t-butylhydrosilyl)amino, and bis(diphenylhydrosilyl)amino groups.

Specific examples of 1-aza-disila-1-cyclohydrocarbyl groups include, butare not limited to, 2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl,2,2,5,5-tetraethyl-1-aza-2,5-disila-1-cyclopentyl,2,2,5,5-tetraphenyl-1-aza-2,5-disila-1-cyclopentyl,2,2,6,6-tetramethyl-1-aza-2,6-disila-1-cyclohexyl,2,2,6,6-tetraethyl-1-aza-2,6-disila-1-cyclohexyl, and2,2,6,6-tetraphenyl-1-aza-2,6-disila-1-cyclohexyl groups.

Specific examples of (trihydrocarbylsilyl)(hydrocarbyl)amino groupsinclude, but are not limited to, (trimethylsilyl)(methyl)amino,(triethylsilyl)(methyl)amino, (triphenylsilyl)(methyl)amino,(trimethylsilyl)(ethyl)amino, (triethylsilyl)(phenyl)amino, and(triisopropylsilyl)(methyl)amino groups.

Specific examples of (dihydrocarbylhydrosilyl)(hydrocarbyl)amino groupsinclude, but are not limited to, (dimethylhydrosilyl)(methyl)amino,(diethylhydrosilyl)(methyl)amino, (diisopropylhydrosilyl)(methyl)amino,(di-n-propylhydrosilyl)(ethyl)amino,(diisobutylhydrosilyl)(phenyl)amino,(di-t-butylhydrosilyl)(phenyl)amino, and(diphenylhydrosilyl)(phenyl)amino groups.

Specific examples of 1-aza-2-sila-1-cyclohydrocarbyl groups include, butare not limited to, 2,2-dimethyl-1-aza-2-sila-1-cyclopentyl,2,2-diethyl-1-aza-2-sila-1-cyclopentyl,2,2-diphenyl-1-aza-2-sila-1-cyclopentyl,2,2-diisopropyl-1-aza-2-sila-1-cyclohexyl,2,2-dibutyl-1-aza-2-sila-1-cyclohexyl, and2,2-diphenyl-1-aza-2-sila-1-cyclohexyl groups.

Specific examples of dihydrocarbylamino groups include, but are notlimited to, dimethylamino, diethylamino, di-n-propylamino,diisopropylamino, di-n-butylamino, diisobutylamino, dicyclohexylamino,diphenylamino, dibenzylamino, (methyl)(cyclohexyl)amino,(ethyl)(cyclohexyl)amino, (methyl)(phenyl)amino, (ethyl)(phenyl)amino,(methyl)(benzyl)amino, and (ethyl)(benzyl)amino groups.

Specific examples of 1-aza-1-cyclohydrocarbyl groups include, but arenot limited to, aziridino, azetidino, pyrrolidino, piperidino,homopiperidino, morpholino, N-methylpiperazino, andN-methylhomopiperazino groups.

In particular embodiments, the nitrile compounds containing a protectedamino group include those compounds where the cyano group is directlyattached to an acyclic moiety. In other particular embodiments, thenitrile compounds containing a protected amino group include thosecompounds where the protected amino group is directly attached to anacyclic moiety. In yet other particular embodiments, the nitrilecompounds include those compounds where both the cyano group and theprotected amino group are directly attached to an acyclic moiety.

In particular embodiments, the nitrile compounds containing a protectedamino group include those compounds where the cyano group is directlyattached to a heterocyclic moiety. In other particular embodiments, thenitrile compounds containing a protected amino group include thosecompounds where the protected amino group is directly attached to aheterocyclic moiety. In yet other particular embodiments, the nitrilecompounds include those compounds where both the cyano group and theprotected amino group are directly attached to a heterocyclic moiety.

In particular embodiments, the nitrile compounds containing a protectedamino group include those compounds where the cyano group is directlyattached to a non-aromatic cyclic moiety. In other particularembodiments, the nitrile compounds containing a protected amino groupinclude those compounds where the protected amino group is directlyattached to a non-aromatic cyclic moiety. In yet other particularembodiments, the nitrile compounds containing a protected amino groupinclude those compounds where both the cyano group and the protectedamino group are directly attached to a non-aromatic cyclic moiety.

In particular embodiments, the nitrile compounds containing a protectedamino group include those compounds where the cyano group is directlyattached to an aromatic moiety (e.g., a phenyl ring) that is devoid ofheteroatoms and the protected amino group is directly attached to anacyclic moiety, a heterocyclic moiety, or a non-aromatic cyclic moiety.

In one or more embodiments, this invention specifically excludes thosecompounds where the cyano group, in other embodiments where theprotected amino group, or in other embodiments where both the cyanogroup and the protected amino group are directly attached to an aromaticmoiety (e.g., a phenyl ring) that is devoid of heteroatoms.

In one or more embodiments, nitrile compounds containing a protectedamino group may be defined by the formula I:

where R¹ is a divalent organic group, and R² and R³ are eachindependently a monovalent organic group or a hydrolyzable group, or R²and R³ join to form a divalent organic group. In one or moreembodiments, the divalent organic group formed by joining R² and R³ mayinclude one or more hydrolyzable groups. In one or more embodiments, thedivalent organic group R¹ may contain one or more additional protectedamino groups and/or one or more additional cyano groups. In one or moreembodiments, where R² and R³ join to form a divalent organic group, thenitrile compound containing a protected amino group may be representedby the formula II:

where R¹ and R⁵ are each independently a divalent organic group, and R⁴and R⁶ are each independently a bond or a hydrolyzable group.

In one or more embodiments, monovalent organic groups may includehydrocarbyl groups or substituted hydrocarbyl groups such as, but notlimited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, allyl,aralkyl, alkaryl, or alkynyl groups. Substituted hydrocarbyl groupsinclude hydrocarbyl groups in which one or more hydrogen atoms have beenreplaced by a substituent such as an alkyl group. In one or moreembodiments, these groups may include from one, or the appropriateminimum number of carbon atoms to form the group, to about 20 carbonatoms. These groups may also contain heteroatoms such as, but notlimited to, nitrogen, boron, oxygen, silicon, sulfur, tin, andphosphorus atoms.

In one or more embodiments, hydrolyzable groups include those groups orsubstituents that are relatively stable, and therefore remain chemicallybonded to the nitrogen atom, in non-aqueous environments or environmentsthat are devoid or substantially devoid of water. However, once exposedto water, moisture, or materials containing water or moisture, thehydrolyzable groups or substituents hydrolyze and are thereby cleavedfrom the nitrogen atom. As a result, the hydrolyzable groups arereplaced by a hydrogen atom.

Exemplary hydrolyzable groups include trihydrocarbylsilyl anddihydrocarbylhydrosilyl groups. Specific examples of trihydrocarbylsilylgroups include trimethylsilyl, triethylsilyl, tri-n-propylsilyl,triisopropylsilyl, tri-n-butylsilyl, triisobutylsilyl, tri-t-butylsilyl,triphenylsilyl, and t-butyldimethylsilyl groups. Specific examples ofdihydrocarbylhydrosilyl groups include dimethylhydrosilyl,diethylhydrosilyl, di-n-propylhydrosilyl, diisopropylhydrosilyl,di-n-butylhydrosilyl, diisobutylhydrosilyl, di-t-butylhydrosilyl, anddiphenylhydrosilyl groups. A catalyst may also be used to remove thesilyl group from the protected amino group. Suitable catalysts includetetrabutylammonium fluoride, strong acids such as hydrochloric acid, andLewis acids such as titanium tetrachloride.

In one or more embodiments, divalent organic groups may includehydrocarbylene groups or substituted hydrocarbylene groups such as, butnot limited to, alkylene, cycloalkylene, alkenylene, cycloalkenylene,alkynylene, cycloalkynylene, or heterocyclic arylene (i.e., arylenegroups with heteroatoms in the ring) groups. In particular embodiments,non-heterocyclic arylene groups (e.g. phenyl groups) are specificallyexcluded; i.e., those arylene groups that do not include a heteroatom inthe ring. Substituted hydrocarbylene groups include hydrocarbylenegroups in which one or more hydrogen atoms have been replaced by asubstituent such as an alkyl group. In one or more embodiments, thesegroups may include from one, or the appropriate minimum number of carbonatoms to form the group, to about 20 carbon atoms. These groups may alsocontain one or more heteroatoms such as, but not limited to, nitrogen,oxygen, boron, silicon, sulfur, tin, and phosphorus atoms.

In one or more embodiments, the divalent organic group R¹ is an acyclicdivalent organic group (either linear or branched) that may or may notinclude one or more heteroatoms. In other embodiments, the divalentorganic group R¹ is a heterocyclic divalent organic group. In yet otherembodiments, the divalent organic group R¹ is a non-aromatic cyclicdivalent organic group that is devoid of heteroatoms.

In one or more embodiments, the divalent organic group R¹ may contain anaromatic ring (e.g. a phenyl ring) that is devoid of heteroatoms so longas the protected amino group is not directly attached to the aromaticring (e.g. the protected amino group can be attached to R¹ via analkylene group pendent from the aromatic ring).

In particular embodiments, R² of formula I is a silyl group, and thenitrile compound containing a protected amino group may be representedby the formula III:

where R¹ is a divalent organic group, R³ is a monovalent organic groupor a hydrolyzable group, each R⁷ is independently a hydrogen atom or amonovalent organic group, or R³ and one R⁷ join to form a divalentorganic group. In one or more embodiments, the divalent organic groupformed by joining R³ and R⁷ may include one or more hydrolyzable groups.In one or more embodiments, where R³ and one R⁷ join to form a divalentorganic group, the nitrile compound containing a protected amino groupmay be represented by the formula IV:

where R¹ and R⁸ are each independently a divalent organic group, andeach R⁷ is independently a hydrogen atom or a monovalent organic group.

In particular embodiments, R² and R³ of formula I are each independentlya silyl group, and the nitrile compound containing a protected aminogroup may be represented by the formula V:

where R¹ is a divalent organic group, and R⁹ and R¹⁰ are eachindependently a hydrogen atom or a monovalent organic group, or at leastone R⁹ and at least one R¹⁰ join to form a divalent organic group. Inone or more embodiments, where one R⁹ and one R¹⁰ join to form adivalent organic group, the nitrile compound containing a protectedamino group may be represented by the formula VI:

where R¹ and R¹¹ are each independently a divalent organic group, and R⁹and R¹⁰ are each independently a hydrogen atom or a monovalent organicgroup.

Exemplary types of nitrile compounds containing a protected amino groupinclude those that may derive from nitrile compounds such asarenecarbonitrile compounds, alkanecarbonitrile compounds,alkenecarbonitrile compounds, alkynecarbonitrile compounds,cycloalkanecarbonitrile compounds, cycloalkenecarbonitrile compounds,cycloalkyne carbonitrile compounds, and heterocyclic nitrile compounds.Those skilled in the art appreciate that arenecarbonitrile compoundsinclude arene compounds where one or more hydrogen atoms on the arenecompound have been replaced by cyano groups, and those skilled in theart appreciate that the other classes of nitrile compounds can besimilarly identified.

Exemplary arenecarbonitrile compounds containing a protected amino groupinclude those that derive from arenecarbonitrile compounds such as,2-methylbenzonitrile, 3-methylbenzonitrile, 4-methylbenzonitrile,2-ethylbenzonitrile, 3-ethylbenzonitrile, 4-ethylbenzonitrile,2-cyclohexylbenzonitrile, 3-cyclohexylbenzonitrile, and4-cyclohexylbenzonitrile.

Exemplary alkanecarbonitrile compounds containing a protected aminogroup include those that derive from alkanecarbonitrile compounds suchas acetonitrile, propionitrile, butyronitrile, isobutyronitrile,valeronitrile, isovaleronitrile, pivalonitrile, 1-hexanenitrile, and1-heptanenitrile.

Exemplary alkenecarbonitrile compounds containing a protected aminogroup include those that derive from alkenecarbonitrile compounds suchas acrylonitrile, methacrylonitrile, crotononitrile, 3-butenenitrile,2-methyl-2-butenenitrile, 2-pentenenitrile, 3-pentenenitrile,4-pentenenitrile, 5-hexenenitrile, 2-methyleneglutaronitrile,6-heptenenitrile, fumaronitrile, methylenemalononitrile, andbenzylidenemalononitrile.

Exemplary alkynecarbonitrile compounds containing a protected aminogroup include those that derive from alkynecarbonitrile compounds suchas 3-butynenitrile, 2-pentynenitrile, 3-pentynenitrile,4-pentynenitrile, and 5-hexynenitrile.

Exemplary cycloalkanecarbonitrile compounds containing a protected aminogroup include those that derive from cycloalkanecarbonitrile compoundssuch as cyclopropanecarbonitrile, cyclobutanecarbonitrile,cyclopentanecarbonitrile, cyclohexanecarbonitrile, andcycloheptanecarbonitrile.

Exemplary cycloalkenecarbonitrile compounds containing a protected aminogroup include those that derive from cycloalkenecarbonitrile compoundssuch as 1-cyclopropenecarbonitrile, 1-cyclobutenecarbonitrile,1-cyclopentenecarbonitrile, 1-cyclohexenecarbonitrile, and1-cycloheptenecarbonitrile.

Exemplary heterocyclic nitrile compounds containing a protected aminogroup include those that derive from heterocyclic nitrile compounds suchas 2-pyridinecarbonitrile, 3-pyridinecarbonitrile,4-pyridinecarbonitrile, 2-pyrimidinecarbonitrile,4-pyrimidinecarbonitrile, 5-pyrimidinecarbonitrile,pyrazinecarbonitrile, 3-pyridazinecarbonitrile, and4-pyridazinecarbonitrile.

Exemplary types of arenecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]arenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]arenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)arenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]arenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]arenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)arenecarbonitrile,(dihydrocarbylamino)arenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)arenecarbonitrile.

Exemplary types of alkanecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]alkanecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkanecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkanecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkanecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkanecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkanecarbonitrile,(dihydrocarbylamino)alkanecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkanecarbonitrile.

Exemplary types of alkenecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]alkenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkenecarbonitrile,(dihydrocarbylamino)alkenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkenecarbonitrile.

Exemplary types of alkynecarbonitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]alkynecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkynecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkynecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkynecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkynecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkynecarbonitrile,(dihydrocarbylamino)alkynecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkynecarbonitrile.

Exemplary types of cycloalkanecarbonitrile compounds containing aprotected amino group include[bis(trihydrocarbylsilyl)amino]cycloalkanecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkanecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkanecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkanecarbonitrile,(dihydrocarbylamino)cycloalkanecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkanecarbonitrile.

Exemplary types of cycloalkenecarbonitrile compounds containing aprotected amino group include[bis(trihydrocarbylsilyl)amino]cycloalkenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkenecarbonitrile,(dihydrocarbylamino)cycloalkenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkenecarbonitrile.

Exemplary types of cycloalkynecarbonitrile compounds containing aprotected amino group include[bis(trihydrocarbylsilyl)amino]cycloalkynecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkynecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkynecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkynecarbonitrile,(dihydrocarbylamino)cycloalkynecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkynecarbonitrile.

Exemplary types of heterocyclic nitrile compounds containing a protectedamino group include [bis(trihydrocarbylsilyl)amino]heterocyclic nitrile,[bis(dihydrocarbylhydrosilyl)amino]heterocyclic nitrile,(1-aza-disila-1-cyclohydrocarbyl)heterocyclic nitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]heterocyclic nitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]heterocyclic nitrile,(1-aza-2-sila-1-cyclohydrocarbyl)heterocyclic nitrile,(dihydrocarbylamino)heterocyclic nitrile, and(1-aza-1-cyclohydrocarbyl)heterocyclic nitrile.

Specific examples of arenecarbonitrile compounds containing a protectedamino group include 2-[bis(trimethylsilyl)aminomethyl]benzonitrile,3-[bis(trimethylsilyl)aminomethyl]benzonitrile,4-[bis(trimethylsilyl)aminomethyl]benzonitrile,2-[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)methyl]benzonitrile,3-[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)methyl]benzonitrile,4-[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)methyl]benzonitrile,2-[(trimethylsilyl)(methyl)aminomethyl]benzonitrile,3-[(trimethylsilyl)(methyl)aminomethyl]benzonitrile,4-[(trimethylsilyl)(methyl)aminomethyl]benzonitrile,2-[(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)methyl]benzonitrile,3-[(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)methyl]benzonitrile,4-[(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)methyl]benzonitrile,2-(dimethylaminomethyl)benzonitrile,3-(dimethylaminomethyl)benzonitrile,4-(dimethylaminomethyl)benzonitrile, 2-(aziridinomethyl)benzonitrile,3-(aziridinomethyl)benzonitrile, 4-(aziridinomethyl)benzonitrile,2-(azetidinomethyl)benzonitrile, 3-(azetidinomethyl)benzonitrile,4-(azetidinomethyl)benzonitrile, 2-(pyrrolidinomethyl)benzonitrile,3-(pyrrolidinomethyl)benzonitrile, 4-(pyrrolidinomethyl)benzonitrile,2-(piperidinomethyl)benzonitrile, 3-(piperidinomethyl)benzonitrile,4-(piperidinomethyl)benzonitrile, 2-(homopiperidinomethyl)benzonitrile,3-(homopiperidinomethyl)benzonitrile,4-(homopiperidinomethyl)benzonitrile, 2-(morpholinomethyl)benzonitrile,3-(morpholinomethyl)benzonitrile, 4-(morpholinomethyl)benzonitrile,2-[(N-methylpiperazino) methyl]benzonitrile, 3-[(N-methylpiperazino)methyl]benzonitrile, 4-[(N-methylpiperazino) methyl]benzonitrile,2-[(N-methylhomopiperazino) methyl]benzonitrile,3-[(N-methylhomopiperazino) methyl]benzonitrile, and4-[(N-methylhomopiperazino) methyl]benzonitrile.

Specific examples of alkanecarbonitrile compounds containing a protectedamino group include [bis(trimethylsilyl)amino]acetonitrile,3-[bis(trimethylsilyl)amino]propionitrile,4-[bis(trimethylsilyl)amino]butyronitrile,5-[bis(trimethylsilyl)amino]valeronitrile,(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)acetonitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)propionitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)butyronitrile,5-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)valeronitrile,[(trimethylsilyl)(methyl)amino]acetonitrile,[(trimethylsilyl)(ethyl)amino]acetonitrile,3-[(trimethylsilyl)(methyl)amino]propionitrile,3-[(trimethylsilyl)(ethyl)amino]propionitrile,4-[(trimethylsilyl)(methyl)amino]butyronitrile,4-[(trimethylsilyl)(ethyl)amino]butyronitrile,5-[(trimethylsilyl)(methyl)amino]valeronitrile,5-[(trimethylsilyl)(ethyl)amino]valeronitrile,N-trimethylsilyl-3,3′-iminodipropionitrile,N-trimethylsilyliminodiacetonitrile,(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)acetonitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)propionitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)butyronitrile,5-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)valeronitrile,(dimethylamino)acetonitrile, (diethylamino)acetonitrile,(diphenylamino)acetonitrile, 3-(dimethylamino)propionitrile,3-(diethylamino)propionitrile, 3-(di-n-propylamino)propionitrile,3-(diisopropylamino)propionitrile, 3-(di-n-butylamino)propionitrile,3-(diisobutylamino)propionitrile, 3-(dicyclohexylamino)propionitrile,3-(diphenylamino)propionitrile, 3-[bis(cyanoethyl)amino]propionitrile,3-(dibenzylamino)propionitrile,3-[(methyl)(cyclohexyl)amino]propionitrile,3-[(ethyl)(cyclohexyl)amino]propionitrile,3-[(methyl)(phenyl)amino]propionitrile,3-[(ethyl)(phenyl)amino]propionitrile,3-[(methyl)(benzyl)amino]propionitrile,3-[(ethyl)(benzyl)amino]propionitrile, 4-(dimethylamino)butyronitrile,4-(diethylamino)butyronitrile, 4-(di-n-propylamino)butyronitrile,4-(diisopropylamino)butyronitrile, 4-(di-n-butylamino)butyronitrile,4-(diisobutylamino)butyronitrile, 4-(dicyclohexylamino)butyronitrile,4-(diphenylamino)butyronitrile, 4-(dibenzylamino)butyronitrile,4-[(methyl)(cyclohexyl)amino]butyronitrile,4-[(ethyl)(cyclohexyl)amino]butyronitrile,4-[(methyl)(phenyl)amino]butyronitrile,4-[(ethyl)(phenyl)amino]butyronitrile,4-[(methyl)(benzyl)amino]butyronitrile,4-[(ethyl)(benzyl)amino]butyronitrile, 5-(dimethylamino)valeronitrile,5-(diethylamino)valeronitrile, 5-(diphenylamino)valeronitrile,aziridinoacetonitrile, azetidinoacetonitrile, pyrrolidinoacetonitrile,piperidinoacetonitrile, homopiperidinoacetonitrile,morpholinoacetonitrile, (N-methylpiperazino) acetonitrile,(N-methylhomopiperazino)acetonitrile, 3-aziridinopropionitrile,3-azetidinopropionitrile, 3-pyrrolidinopropionitrile,3-piperidinopropionitrile, 3-homopiperidinopropionitrile,3-morpholinopropionitrile, 3-(N-methylpiperazino) propionitrile,3-(N-methylhomopiperazino) propionitrile, 4-aziridinobutyronitrile,4-azetidinobutyronitrile, 4-pyrrolidinobutyronitrile,4-piperidinobutyronitrile, 4-homopiperidinobutyronitrile,4-morpholinobutyronitrile, 4-(N-methylpiperazino)butyronitrile,4-(N-methylhomopiperazino)butyronitrile, 5-aziridinovaleronitrile,5-azetidinovaleronitrile, 5-pyrrolidinovaleronitrile,5-piperidinovaleronitrile, 5-homopiperidinovaleronitrile,5-morpholinovaleronitrile, 5-(N-methylpiperazino)valeronitrile, and5-(N-methylhomopiperazino)valeronitrile.

Specific examples of alkenecarbonitrile compounds containing a protectedamino group include 3-[bis(trimethylsilyl)amino]crotononitrile,3-[bis(trimethylsilyl)amino]-4-pentenenitrile,3-[bis(trimethylsilyl)amino]-5-hexenenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)crotononitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-4-pentenenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-5-hexenenitrile,3-[(trimethylsilyl)(methyl)amino]crotononitrile,3-[(trimethylsilyl)(ethyl)amino]crotononitrile,3-[(trimethylsilyl)(methyl)amino]-4-pentenenitrile,3-[(trimethylsilyl)(ethyl)amino]-4-pentenenitrile,3-[(trimethylsilyl)(methyl)amino]-5-hexenenitrile,3-[(trimethylsilyl)(ethyl)amino]-5-hexenenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)crotononitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-4-pentenenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-5-hexenenitrile,3-(dimethylamino)acrylonitrile, 3-(dimethylamino)crotononitrile,3-(diethylamino)crotononitrile, 3-(di-n-propylamino)crotononitrile,3-(diisopropylamino)crotononitrile, 3-(di-n-butylamino)crotononitrile,3-(diisobutylamino)crotononitrile, 3-(dicyclohexylamino)crotononitrile,3-(diphenylamino)crotononitrile, 3-(dibenzylamino)crotononitrile,3-[(methyl)(cyclohexyl)amino]crotononitrile,3-[(ethyl)(cyclohexyl)amino]crotononitrile,3-[(methyl)(phenyl)amino]crotononitrile,3-[(ethyl)(phenyl)amino]crotononitrile,3-[(methyl)(benzyl)amino]crotononitrile,3-[(ethyl)(benzyl)amino]crotononitrile,3-(dimethylamino)-4-pentenenitrile, 3-(diethylamino)-4-pentenenitrile,3-(di-n-propylamino)-4-pentenenitrile,3-(diisopropylamino)-4-pentenenitrile,3-(di-n-butylamino)-4-pentenenitrile,3-(diisobutylamino)-4-pentenenitrile,3-(dicyclohexylamino)-4-pentenenitrile,3-(diphenylamino)-4-pentenenitrile, 3-(dibenzylamino)-4-pentenenitrile,3-[(methyl)(cyclohexyl)amino]-4-pentenenitrile,3-[(ethyl)(cyclohexyl)amino]-4-pentenenitrile,3-[(methyl)(phenyl)amino]-4-pentenenitrile,3-[(ethyl)(phenyl)amino]-4-pentenenitrile,3-[(methyl)(benzyl)amino]-4-pentenenitrile,3-[(ethyl)(benzyl)amino]-4-pentenenitrile,3-(dimethylamino)-5-hexenenitrile, 3-(diethylamino)-5-hexenenitrile,3-(di-n-propylamino)-5-hexenenitrile,3-(diisopropylamino)-5-hexenenitrile,3-(di-n-butylamino)-5-hexenenitrile,3-(diisobutylamino)-5-hexenenitrile,3-(dicyclohexylamino)-5-hexenenitrile,3-(diphenylamino)-5-hexenenitrile, 3-(dibenzylamino)-5-hexenenitrile,3-[(methyl)(cyclohexyl)amino]-5-hexenenitrile,3-[(ethyl)(cyclohexyl)amino]-5-hexenenitrile,3-[(methyl)(phenyl)amino]-5-hexenenitrile,3-[(ethyl)(phenyl)amino]-5-hexenenitrile,3-[(methyl)(benzyl)amino]-5-hexenenitrile,3-[(ethyl)(benzyl)amino]-5-hexenenitrile, 3-aziridinocrotononitrile,3-azetidinocrotononitrile, 3-pyrrolidinocrotononitrile,3-piperidinocrotononitrile, 3-homopiperidinocrotononitrile,3-morpholinocrotononitrile, 3-(N-methylpiperazino) crotononitrile,3-(N-methylhomopiperazino) crotononitrile, 3-aziridino-4-pentenenitrile,3-azetidino-4-pentenenitrile, 3-pyrrolidino-4-pentenenitrile,3-piperidino-4-pentenenitrile, 3-homopiperidino-4-pentenenitrile,3-morpholino-4-pentenenitrile, 3-(N-methylpiperazino)-4-pentenenitrile,3-(N-methylhomopiperazino)-4-pentenenitrile,3-aziridino-5-hexenenitrile, 3-azetidino-5-hexenenitrile,3-pyrrolidino-5-hexenenitrile, 3-piperidino-5-hexenenitrile,3-homopiperidino-5-hexenenitrile, 3-morpholino-5-hexenenitrile,3-(N-methylpiperazino)-5-hexenenitrile, and3-(N-methylhomopiperazino)-5-hexenenitrile.

Specific alkynecarbonitrile compounds containing protected amino groupsinclude 3-[bis(trimethylsilyl)amino]-4-pentynenitrile,3-[bis(trimethylsilyl)amino]-5-hexynenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-4-pentynenitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-5-hexynenitrile,3-[(trimethylsilyl)(methyl)amino]-4-pentynenitrile,3-[(trimethylsilyl)(ethyl)amino]-4-pentynenitrile,3-[(trimethylsilyl)(methyl)amino]-5-hexynenitrile,3-[(trimethylsilyl)(ethyl)amino]-5-hexynenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-4-pentynenitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-5-hexynenitrile,3-(dimethylamino)-4-pentynenitrile, 3-(diethylamino)-4-pentynenitrile,3-(di-n-propylamino)-4-pentynenitrile,3-(diisopropylamino)-4-pentynenitrile,3-(di-n-butylamino)-4-pentynenitrile,3-(diisobutylamino)-4-pentynenitrile,3-(dicyclohexylamino)-4-pentynenitrile,3-(diphenylamino)-4-pentynenitrile, 3-(dibenzylamino)-4-pentynenitrile,3-[(methyl)(cyclohexyl)amino]-4-pentynenitrile,3-[(ethyl)(cyclohexyl)amino]-4-pentynenitrile,3-[(methyl)(phenyl)amino]-4-pentynenitrile,3-[(ethyl)(phenyl)amino]-4-pentynenitrile,3-[(methyl)(benzyl)amino]-4-pentynenitrile,3-[(ethyl)(benzyl)amino]-4-pentynenitrile,3-(dimethylamino)-5-hexynenitrile, 3-(diethylamino)-5-hexynenitrile,3-(di-n-propylamino)-5-hexynenitrile,3-(diisopropylamino)-5-hexynenitrile,3-(di-n-butylamino)-5-hexynenitrile,3-(diisobutylamino)-5-hexynenitrile,3-(dicyclohexylamino)-5-hexynenitrile,3-(diphenylamino)-5-hexynenitrile, 3-(dibenzylamino)-5-hexynenitrile,3-[(methyl)(cyclohexyl)amino]-5-hexynenitrile,3-[(ethyl)(cyclohexyl)amino]-5-hexynenitrile,3-[(methyl)(phenyl)amino]-5-hexynenitrile,3-[(ethyl)(phenyl)amino]-5-hexynenitrile,3-[(methyl)(benzyl)amino]-5-hexynenitrile,3-[(ethyl)(benzyl)amino]-5-hexynenitrile, 3-aziridino-4-pentynenitrile,3-azetidino-4-pentynenitrile, 3-pyrrolidino-4-pentynenitrile,3-piperidino-4-pentynenitrile, 3-homopiperidino-4-pentynenitrile,3-morpholino-4-pentynenitrile, 3-(N-methylpiperazino)-4-pentynenitrile,3-(N-methylhomopiperazino)-4-pentynenitrile,3-aziridino-5-hexynenitrile, 3-azetidino-5-hexynenitrile,3-pyrrolidino-5-hexynenitrile, 3-piperidino-5-hexynenitrile,3-homopiperidino-5-hexynenitrile, 3-morpholino-5-hexynenitrile,3-(N-methylpiperazino)-5-hexynenitrile, and3-(N-methylhomopiperazino)-5-hexynenitrile.

Specific examples of cycloalkanecarbonitrile compounds containing aprotected amino group include3-[bis(trimethylsilyl)amino]cyclopentanecarbonitrile,4-[bis(trimethylsilyl)amino]cyclohexanecarbonitrile,3-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclopentanecarbonitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclohexanecarbonitrile,3-[(trimethylsilyl)(methyl)amino]cyclopentanecarbonitrile,3-[(trimethylsilyl)(ethyl)amino]cyclopentanecarbonitrile,4-[(trimethylsilyl)(methyl)amino]cyclohexanecarbonitrile,4-[(trimethylsilyl)(ethyl)amino]cyclohexanecarbonitrile,3-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclopentanecarbonitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclohexanecarbonitrile,3-(3-dimethylaminophenyl)cyclopropane-1,1,2,2-tetracarbonitrile,3-(dimethylamino)cyclopentanecarbonitrile,3-(diethylamino)cyclopentanecarbonitrile,3-(di-n-propylamino)cyclopentanecarbonitrile,3-(diisopropylamino)cyclopentanecarbonitrile,3-(di-n-butylamino)cyclopentanecarbonitrile,3-(diisobutylamino)cyclopentanecarbonitrile,3-(dicyclohexylamino)cyclopentanecarbonitrile,3-(diphenylamino)cyclopentanecarbonitrile,3-(dibenzylamino)cyclopentanecarbonitrile,3-[(methyl)(cyclohexyl)amino]cyclopentanecarbonitrile,3-[(ethyl)(cyclohexyl)amino]cyclopentanecarbonitrile,3-[(methyl)(phenyl)amino]cyclopentanecarbonitrile,3-[(ethyl)(phenyl)amino]cyclopentanecarbonitrile,3-[(methyl)(benzyl)amino]cyclopentanecarbonitrile,3-[(ethyl)(benzyl)amino]cyclopentanecarbonitrile,4-(dimethylamino)cyclohexanecarbonitrile,4-(diethylamino)cyclohexanecarbonitrile,4-(di-n-propylamino)cyclohexanecarbonitrile,4-(diisopropylamino)cyclohexanecarbonitrile,4-(di-n-butylamino)cyclohexanecarbonitrile,4-(diisobutylamino)cyclohexanecarbonitrile,3-(dicyclohexylamino)cyclohexanecarbonitrile,4-(diphenylamino)cyclohexanecarbonitrile,4-(dibenzylamino)cyclohexanecarbonitrile,4-[(methyl)(cyclohexyl)amino]cyclohexanecarbonitrile,4-[(ethyl)(cyclohexyl)amino]cyclohexanecarbonitrile,4-[(methyl)(phenyl)amino]cyclohexanecarbonitrile,4-[(ethyl)(phenyl)amino]cyclohexanecarbonitrile,4-[(methyl)(benzyl)amino]cyclohexanecarbonitrile,4-[(ethyl)(benzyl)amino]cyclohexanecarbonitrile,4-aziridinocyclopentanecarbonitrile,3-azetidinocyclopentanecarbonitrile,3-pyrrolidinocyclopentanecarbonitrile,3-piperidinocyclopentanecarbonitrile,3-homopiperidinocyclopentanecarbonitrile,3-morpholinocyclopentanecarbonitrile,3-(N-methylpiperazino)cyclopentanecarbonitrile,3-(N-methylhomopiperazino)cyclopentanecarbonitrile,4-aziridinocyclohexanecarbonitrile, 4-azetidinocyclohexanecarbonitrile,4-pyrrolidinocyclohexanecarbonitrile,4-piperidinocyclohexanecarbonitrile,4-homopiperidinocyclohexanecarbonitrile,4-morpholinocyclohexanecarbonitrile,4-(N-methylpiperazino)cyclohexanecarbonitrile, and4-(N-methylhomopiperazino)cyclohexanecarbonitrile.

Specific examples of cycloalkenecarbonitrile compounds containing aprotected amino group include4-[bis(trimethylsilyl)amino]cyclopentene-1-carbonitrile,4-[bis(trimethylsilyl)amino]cyclohexene-1-carbonitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclopentene-1-carbonitrile,4-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)cyclohexene-1-carbonitrile,4-[(trimethylsilyl)(methyl)amino]cyclopentene-1-carbonitrile,4-[(trimethylsilyl)(ethyl)amino]cyclopentene-1-carbonitrile,4-[(trimethylsilyl)(methyl)amino]cyclohexene-1-carbonitrile,4-[(trimethylsilyl)(ethyl)amino]cyclohexene-1-carbonitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclopentene-1-carbonitrile,4-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)cyclohexene-1-carbonitrile,4-(dimethylamino)cyclopentene-1-carbonitrile,4-(diethylamino)cyclopentene-1-carbonitrile,4-(di-n-propylamino)cyclopentene-1-carbonitrile,4-(diisopropylamino)cyclopentene-1-carbonitrile,4-(di-n-butylamino)cyclopentene-1-carbonitrile,4-(diisobutylamino)cyclopentene-1-carbonitrile,4-(dicyclohexylamino)cyclopentene-1-carbonitrile,4-(diphenylamino)cyclopentene-1-carbonitrile,4-(dibenzylamino)cyclopentene-1-carbonitrile,4-[(methyl)(cyclohexyl)amino]cyclopentene-1-carbonitrile,4-[(ethyl)(cyclohexyl)amino]cyclopentene-1-carbonitrile,4-[(methyl)(phenyl)amino]cyclopentene-1-carbonitrile,4-[(ethyl)(phenyl)amino]cyclopentene-1-carbonitrile,4-[(methyl)(benzyl)amino]cyclopentene-1-carbonitrile,4-[(ethyl)(benzyl)amino]cyclopentene-1-carbonitrile,4-(dimethylamino)cyclohexene-1-carbonitrile,4-(diethylamino)cyclohexene-1-carbonitrile,4-(di-n-propylamino)cyclohexene-1-carbonitrile,4-(diisopropylamino)cyclohexene-1-carbonitrile,4-(di-n-butylamino)cyclohexene-1-carbonitrile,4-(diisobutylamino)cyclohexene-1-carbonitrile,4-(dicyclohexylamino)cyclohexene-1-carbonitrile,4-(diphenylamino)cyclohexene-1-carbonitrile,4-(dibenzylamino)cyclohexene-1-carbonitrile,4-[(methyl)(cyclohexyl)amino]cyclohexene-1-carbonitrile,4-[(ethyl)(cyclohexyl)amino]cyclohexene-1-carbonitrile,4-[(methyl)(phenyl)amino]cyclohexene-1-carbonitrile,4-[(ethyl)(phenyl)amino]cyclohexene-1-carbonitrile,4-[(methyl)(benzyl)amino]cyclohexene-1-carbonitrile,4-[(ethyl)(benzyl)amino]cyclohexene-1-carbonitrile,4-aziridinocyclopentene-1-carbonitrile,4-azetidinocyclopentene-1-carbonitrile,4-pyrrolidinocyclopentene-1-carbonitrile,4-piperidinocyclopentene-1-carbonitrile,4-homopiperidinocyclopentene-1-carbonitrile,4-morpholinocyclopentene-1-carbonitrile, 4-(N-methylpiperazino)cyclopentene-1-carbonitrile, 4-(N-methylhomopiperazino)cyclopentene-1-carbonitrile, 4-aziridinocyclohexene-1-carbonitrile,4-azetidinocyclohexene-1-carbonitrile,4-pyrrolidinocyclohexene-1-carbonitrile,4-piperidinocyclohexene-1-carbonitrile,4-homopiperidinocyclohexene-1-carbonitrile,4-morpholinocyclohexene-1-carbonitrile, 4-(N-methylpiperazino)cyclohexene-1-carbonitrile, and 4-(N-methylhomopiperazino)cyclohexene-1-carbonitrile.

Specific examples of heterocyclic nitrile compounds containing aprotected amino group include5-[bis(trimethylsilyl)amino]-2-pyridinecarbonitrile,5-[bis(trimethylsilyl)amino]-2-pyrimidinecarbonitrile,5-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-2-pyridinecarbonitrile,5-(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)-2-pyrimidinecarbonitrile,5-[(trimethylsilyl)(methyl)amino]-2-pyridinecarbonitrile,5-[(trimethylsilyl)(ethyl)amino]-2-pyridinecarbonitrile,5-[(trimethylsilyl)(methyl)amino]-2-pyrimidinecarbonitrile,5-[(trimethylsilyl)(ethyl)amino]-2-pyrimidinecarbonitrile,5-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-2-pyridinecarbonitrile,5-(2,2-dimethyl-1-aza-2-sila-1-cyclopentyl)-2-pyrimidinecarbonitrile,5-(dimethylamino)-2-pyridinecarbonitrile,3-(diethylamino)-2-pyridinecarbonitrile,5-(di-n-propylamino)-2-pyridinecarbonitrile,5-(diisopropylamino)-2-pyridinecarbonitrile,5-(di-n-butylamino)-2-pyridinecarbonitrile,5-(diisobutylamino)-2-pyridinecarbonitrile,5-(dicyclohexylamino)-2-pyridinecarbonitrile,5-(diphenylamino)-2-pyridinecarbonitrile,5-(dibenzylamino)-2-pyridinecarbonitrile,5-[(methyl)(cyclohexyl)amino]-2-pyridinecarbonitrile,5-[(ethyl)(cyclohexyl)amino]-2-pyridinecarbonitrile,5-[(methyl)(phenyl)amino]-2-pyridinecarbonitrile,5-[(ethyl)(phenyl)amino]-2-pyridinecarbonitrile,5-[(methyl)(benzyl)amino]-2-pyridinecarbonitrile,5-[(ethyl)(benzyl)amino]-2-pyridinecarbonitrile,5-(dimethylamino)-2-pyrimidinecarbonitrile,5-(diethylamino)-2-pyrimidinecarbonitrile,5-(di-n-propylamino)-2-pyrimidinecarbonitrile,5-(diisopropylamino)-2-pyrimidinecarbonitrile,5-(di-n-butylamino)-2-pyrimidinecarbonitrile,5-(diisobutylamino)-2-pyrimidinecarbonitrile,5-(dicyclohexylamino)-2-pyrimidinecarbonitrile,5-(diphenylamino)-2-pyrimidinecarbonitrile,5-(dibenzylamino)-2-pyrimidinecarbonitrile,5-[(methyl)(cyclohexyl)amino]-2-pyrimidinecarbonitrile,5-[(ethyl)(cyclohexyl)amino]-2-pyrimidinecarbonitrile,5-[(methyl)(phenyl)amino]-2-pyrimidinecarbonitrile,5-[(ethyl)(phenyl)amino]-2-pyrimidinecarbonitrile,5-[(methyl)(benzyl)amino]-2-pyrimidinecarbonitrile,5-[(ethyl)(benzyl)amino]-2-pyrimidinecarbonitrile,5-aziridino-2-pyridinecarbonitrile, 5-azetidino-2-pyridinecarbonitrile,5-pyrrolidino-2-pyridinecarbonitrile,5-piperidino-2-pyridinecarbonitrile,5-homopiperidino-2-pyridinecarbonitrile,5-morpholino-2-pyridinecarbonitrile,5-(N-methylpiperazino)-2-pyridinecarbonitrile,5-(N-methylhomopiperazino)-2-pyridinecarbonitrile,5-aziridino-2-pyrimidinecarbonitrile,5-azetidino-2-pyrimidinecarbonitrile,5-pyrrolidino-2-pyrimidinecarbonitrile,5-piperidino-2-pyrimidinecarbonitrile,5-homopiperidino-2-pyrimidinecarbonitrile,5-morpholino-2-pyrimidinecarbonitrile,5-(N-methylpiperazino)-2-pyrimidinecarbonitrile, and5-(N-methylhomopiperazino)-2-pyrimidinecarbonitrile.

In one or more embodiments, the nitrile compounds containing a protectedamino group can be synthesized by alkylating or silylating a nitrilecompound containing a primary amino group (i.e. —NH₂) or a secondaryamino group represented by the formula —NH(R), where R is a monovalentorganic group such as a hydrocarbyl or silyl group. Exemplary alkylatingreagents include alkyl halides. Exemplary silylating reagents includetrialkylsilyl halides, 1,2-bis(chlorodimethylsilyl)ethane, andtrialkylsilyl trifluoromethanesulfonate. A base such as triethylaminemay be used to neutralize the acid formed during the alkylation orsilylation reaction.

The amount of the nitrile compound containing a protected amino groupthat can be added to the polymerization mixture to yield thefunctionalized polymer of this invention may depend on various factorsincluding the type and amount of initiator used to synthesize thereactive polymer and the desired degree of functionalization. In one ormore embodiments, the amount of the nitrile compound containing aprotected amino group employed can be described with reference to theamount of the metal cation associated with the initiator. For example,where an organolithium initiator is employed, the molar ratio of thenitrile compound containing a protected amino group to the lithiumcation may be from about 0.3:1 to about 2:1, in other embodiments fromabout 0.6:1 to about 1.5:1, and in other embodiments from 0.8:1 to about1.2:1.

In one or more embodiments, in addition to the nitrile compoundcontaining a protected amino group, a co-functionalizing agent may alsobe added to the polymerization mixture to yield a functionalized polymerwith tailored properties. A mixture of two or more co-functionalizingagents may also be employed. The co-functionalizing agent may be addedto the polymerization mixture prior to, together with, or after theintroduction of the nitrile compound. In one or more embodiments, theco-functionalizing agent is added to the polymerization mixture at least5 minutes after, in other embodiments at least 10 minutes after, and inother embodiments at least 30 minutes after the introduction of thenitrile compound.

In one or more embodiments, co-functionalizing agents include compoundsor reagents that can react with a reactive polymer produced by thisinvention and thereby provide the polymer with a functional group thatis distinct from a propagating chain that has not been reacted with theco-functionalizing agent. The functional group may be reactive orinteractive with other polymer chains (propagating and/ornon-propagating) or with other constituents such as reinforcing fillers(e.g. carbon black) that may be combined with the polymer. In one ormore embodiments, the reaction between the co-functionalizing agent andthe reactive polymer proceeds via an addition or substitution reaction.

Useful co-functionalizing agents may include compounds that simplyprovide a functional group at the end of a polymer chain without joiningtwo or more polymer chains together, as well as compounds that cancouple or join two or more polymer chains together via a functionallinkage to form a single macromolecule. The latter type ofco-functionalizing agents may also be referred to as coupling agents.

In one or more embodiments, co-functionalizing agents include compoundsthat will add or impart a heteroatom to the polymer chain. In particularembodiments, co-functionalizing agents include those compounds that willimpart a functional group to the polymer chain to form a functionalizedpolymer that reduces the 50° C. hysteresis loss of a carbon-black filledvulcanizates prepared from the functionalized polymer as compared tosimilar carbon-black filled vulcanizates prepared fromnon-functionalized polymer. In one or more embodiments, this reductionin hysteresis loss is at least 5%, in other embodiments at least 10%,and in other embodiments at least 15%.

In one or more embodiments, suitable co-functionalizing agents includethose compounds that contain groups that may react with the reactivepolymers produced in accordance with this invention. Exemplaryco-functionalizing agents include ketones, quinones, aldehydes, amides,esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones,aminothioketones, and acid anhydrides. Examples of these compounds aredisclosed in U.S. Pat. Nos. 4,906,706, 4,990,573, 5,064,910, 5,567,784,5,844,050, 6838,526, 6977,281, and 6,992,147; U.S. Pat. Publication Nos.2006/0004131 A1, 2006/0025539 A1, 2006/0030677 A1, and 2004/0147694 A1;Japanese Patent Application Nos. 05-051406A, 05-059103A, 10-306113A, and11-035633A; which are incorporated herein by reference. Other examplesof co-functionalizing agents include azine compounds as described inU.S. Ser. No. 11/640,711, hydrobenzamide compounds as disclosed in U.S.Ser. No. 11/710,713, nitro compounds as disclosed in U.S. Ser. No.11/710,845, and protected oxime compounds as disclosed in U.S. Ser. No.60/875,484, all of which are incorporated herein by reference.

In particular embodiments, the co-functionalizing agents employed may bemetal halides, metalloid halides, alkoxysilanes, metal carboxylates,hydrocarbylmetal carboxylates, hydrocarbylmetal ester-carboxylates, andmetal alkoxides.

Exemplary metal halide compounds include tin tetrachloride, tintetrabromide, tin tetraiodide, n-butyltin trichloride, phenyltintrichloride, di-n-butyltin dichloride, diphenyltin dichloride,tri-n-butyltin chloride, triphenyltin chloride, germanium tetrachloride,germanium tetrabromide, germanium tetraiodide, n-butylgermaniumtrichloride, di-n-butylgermanium dichloride, and tri-n-butylgermaniumchloride.

Exemplary metalloid halide compounds include silicon tetrachloride,silicon tetrabromide, silicon tetraiodide, methyltrichlorosilane,phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane,boron trichloride, boron tribromide, boron triiodide, phosphoroustrichloride, phosphorous tribromide, and phosphorus triiodide.

In one or more embodiments, the alkoxysilanes may include at least onegroup selected from the group consisting of an epoxy group and anisocyanate group.

Exemplary alkoxysilane compounds including an epoxy group include(3-glycidyloxypropyl)trimethoxysilane,(3-glycidyloxypropyl)triethoxysilane,(3-glycidyloxypropyl)triphenoxysilane,(3-glycidyloxypropyl)methyldimethoxysilane,(3-glycidyloxypropyl)methyldiethoxysilane,(3-glycidyloxypropyl)methyldiphenoxysilane,[2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane, and[2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane.

Exemplary alkoxysilane compounds including an isocyanate group include(3-isocyanatopropyl)trimethoxysilane,(3-isocyanatopropyl)triethoxysilane,(3-isocyanatopropyl)triphenoxysilane,(3-isocyanatopropyl)methyldimethoxysilane,(3-isocyanatopropyl)methyldiethoxysilane(3-isocyanatopropyl)methyldiphenoxysilane, and(isocyanatomethyl)methyldimethoxysilane.

Exemplary metal carboxylate compounds include tin tetraacetate, tinbis(2-ethylhexanaote), and tin bis(neodecanoate).

Exemplary hydrocarbylmetal carboxylate compounds include triphenyltin2-ethylhexanoate, tri-n-butyltin 2-ethylhexanoate, tri-n-butyltinneodecanoate, triisobutyltin 2-ethylhexanoate, diphenyltinbis(2-ethylhexanoate), di-n-butyltin bis(2-ethylhexanoate),di-n-butyltin bis(neodecanoate), phenyltin tris(2-ethylhexanoate), andn-butylltin tris(2-ethylhexanoate).

Exemplary hydrocarbylmetal ester-carboxylate compounds includedi-n-butyltin bis(n-octylmaleate), di-n-octyltin bis(n-octylmaleate),diphenyltin bis(n-octylmaleate), di-n-butyltin bis(2-ethylhexylmaleate),di-n-octyltin bis(2-ethylhexylmaleate), and diphenyltinbis(2-ethylhexylmaleate).

Exemplary metal alkoxide compounds include dimethoxytin, diethoxytin,tetraethoxytin, tetra-n-propoxytin, tetraisopropoxytin,tetra-n-butoxytin, tetraisobutoxytin, tetra-t-butoxytin, andtetraphenoxytin.

The amount of the co-functionalizing agent that can be added to thepolymerization mixture may depend on various factors including the typeand amount of initiator used to synthesize the reactive polymer and thedesired degree of functionalization. In one or more embodiments, theamount of the nitrile compound containing a protected amino groupemployed can be described with reference to the amount of metal cationassociated with the initiator. For example, where an organolithiuminitiator is employed, the molar ratio of the nitrile containing aprotected amino group to the lithium cation may be from about 0.3:1 toabout 2:1, in other embodiments from about 0.6:1 to about 1.5:1, and inother embodiments from 0.8:1 to about 1.2:1.

The amount of the co-functionalizing agent employed can also bedescribed with reference to the nitrile compound containing a protectedamino group. In one or more embodiments, the molar ratio of theco-functionalizing agent to the nitrile compound may be from about0.05:1 to about 1:1, in other embodiments from about 0.1:1 to about0.8:1, and in other embodiments from about 0.2:1 to about 0.6:1.

In one or more embodiments, the nitrile compound containing a protectedamino group (and optionally the co-functionalizing agent) may beintroduced to the polymerization mixture at a location (e.g., within avessel) where the polymerization has been conducted. In otherembodiments, the nitrile compound may be introduced to thepolymerization mixture at a location that is distinct from where thepolymerization has taken place. For example, the nitrile compound may beintroduced to the polymerization mixture in downstream vessels includingdownstream reactors or tanks, in-line reactors or mixers, extruders, ordevolatilizers.

In one or more embodiments, the nitrile compound containing a protectedamino group (and optionally the co-functionalizing agent) can be reactedwith the reactive polymer after a desired monomer conversion is achievedbut before the polymerization mixture is quenched by a quenching agent.In one or more embodiments, the reaction between the nitrile compoundand the reactive polymer may take place within 30 minutes, in otherembodiments within 5 minutes, and in other embodiments within one minuteafter the peak polymerization temperature is reached. In one or moreembodiments, the reaction between the nitrile compound and the reactivepolymer can occur once the peak polymerization temperature is reached.In other embodiments, the reaction between the nitrile compound and thereactive polymer can occur after the reactive polymer has been stored.In one or more embodiments, the storage of the reactive polymer occursat room temperature or below room temperature under an inert atmosphere.In one or more embodiments, the reaction between the nitrile compoundand the reactive polymer may take place at a temperature from about 10°C. to about 150° C., and in other embodiments from about 20° C. to about100° C. The time required for completing the reaction between thenitrile compound and the reactive polymer depends on various factorssuch as the type and amount of the initiator used to prepare thereactive polymer, the type and amount of the nitrile compound, as wellas the temperature at which the functionalization reaction is conducted.In one or more embodiments, the reaction between the nitrile compoundand the reactive polymer can be conducted for about 10 to 60 minutes.

In one or more embodiments, after the reaction between the reactivepolymer and the nitrile compound containing a protected amino group (andoptionally the co-functionalizing agent) has been accomplished orcompleted, a quenching agent can be added to the polymerization mixturein order to protonate the reaction product between the reactive polymerand the nitrile compound, inactivate any residual reactive polymerchains, and/or inactivate the initiator. The quenching agent may includea protic compound, which includes, but is not limited to, an alcohol, acarboxylic acid, an inorganic acid, water, or a mixture thereof. Anantioxidant such as 2,6-di-tert-butyl-4-methylphenol may be added alongwith, before, or after the addition of the quenching agent. The amountof the antioxidant employed may be in the range of 0.2% to 1% by weightof the polymer product. Additionally, the polymer product can be oilextended by adding an oil to the polymer, which may be in the form of apolymer cement or polymer dissolved or suspended in monomer. Practice ofthe present invention does not limit the amount of oil that may beadded, and therefore conventional amounts may be added (e.g., 5-50 phr).Useful oils or extenders that may be employed include, but are notlimited to, aromatic oils, paraffinic oils, naphthenic oils, vegetableoils other than castor oils, low PCA oils including MES, TDAE, and SRAE,and heavy naphthenic oils.

Once the polymerization mixture has been quenched, the variousconstituents of the polymerization mixture may be recovered. In one ormore embodiments, the unreacted monomer can be recovered from thepolymerization mixture. For example, the monomer can be distilled fromthe polymerization mixture by using techniques known in the art. In oneor more embodiments, a devolatilizer may be employed to remove themonomer from the polymerization mixture. Once the monomer has beenremoved from the polymerization mixture, the monomer may be purified,stored, and/or recycled back to the polymerization process.

The polymer product may be recovered from the polymerization mixture byusing techniques known in the art. In one or more embodiments,desolventization and drying techniques may be used. For instance, thepolymer can be recovered by passing the polymerization mixture through aheated screw apparatus, such as a desolventizing extruder, in which thevolatile substances are removed by evaporation at appropriatetemperatures (e.g., about 100° C. to about 170° C.) and underatmospheric or sub-atmospheric pressure. This treatment serves to removeunreacted monomer as well as any low-boiling solvent. Alternatively, thepolymer can also be recovered by subjecting the polymerization mixtureto steam desolventization, followed by drying the resulting polymercrumbs in a hot air tunnel. The polymer can also be recovered bydirectly drying the polymerization mixture on a drum dryer.

While the reactive polymer and the nitrile compound containing aprotected amino group (and optionally the co-functionalizing agent) arebelieved to react to produce a novel functionalized polymer, which canbe protonated or further modified, the exact chemical structure of thefunctionalized polymer produced in every embodiment is not known withany great degree of certainty, particularly as the structure relates tothe residue imparted to the polymer chain end by the nitrile compoundand optionally the co-functionalizing agent. Indeed, it is speculatedthat the structure of the functionalized polymer may depend upon variousfactors such as the conditions employed to prepare the reactive polymer(e.g., the type and amount of the initiator) and the conditions employedto react the nitrile compound (and optionally the co-functionalizingagent) with the reactive polymer (e.g., the types and amounts of thenitrile compound and the co-functionalizing agent).

In one or more embodiments, one of the products resulting from thereaction between the reactive polymer and the nitrile compoundcontaining a protected amino group, particularly after reaction with aquenching agent, may be a functionalized polymer containing a protectedamino group, which is defined by the formula VII:

where π is a polymer chain of a polydiene or a copolymer of conjugateddiene and co-monomer having a medium or low cis-1,4-linkage content, R¹is a divalent organic group, and R² and R³ are each independently amonovalent organic group or a hydrolyzable group, or R² and R³ join toform a divalent organic group, with the proviso that R¹ is an acyclicdivalent organic group, a heterocyclic divalent organic group, anon-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theprotected amino group (i.e. the —N(R²)(R³) group in the formula VII) isnot directly attached to the aromatic ring.

It is believed that, upon exposure to water, moisture, or materialscontaining water or moisture, the functionalized polymer described byformula VII may undergo a hydrolysis reaction, which may optionally becatalyzed by the use of an acid, to form a functionalized polymercontaining an amino group, which is defined by the formula VIII:

where π is a polymer chain of a polydiene or a copolymer of conjugateddiene and co-monomer having a medium or low cis-1,4-linkage content, R¹is a divalent organic group, and R¹² and R¹³ are each independently amonovalent organic group or a hydrogen atom, or R¹² and R¹³ join to forma divalent organic group, with the proviso that R¹ is an acyclicdivalent organic group, a heterocyclic divalent organic group, anon-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theamino group (i.e. the —N(R¹²)(R¹³) group in the formula VIII) is notdirectly attached to the aromatic ring.

In one or more embodiments, the functionalized polymers preparedaccording to this invention may contain unsaturation. In these or otherembodiments, the functionalized polymers are vulcanizable. In one ormore embodiments, the functionalized polymers can have a glasstransition temperature (T_(g)) that is less than 0° C., in otherembodiments less than −20° C., and in other embodiments less than −30°C. In one embodiment, these polymers may exhibit a single glasstransition temperature. In particular embodiments, the polymers may behydrogenated or partially hydrogenated.

The number average molecular weight (M_(n)) of the functionalizedpolymers prepared according to this invention may be from about 1,000 toabout 1,000,000, in other embodiments from about 5,000 to about1,000,000, in other embodiments from about 50,000 to about 500,000, andin other embodiments from about 100,000 to about 300,000, as determinedby using gel permeation chromatography (GPC) calibrated with polystyrenestandards and Mark-Houwink constants for the polymer in question. Themolecular weight distribution or polydispersity (M_(w)/M_(n)) of thesepolymers may be from about 1.0 to about 3.0, and in other embodimentsfrom about 1.1 to about 2.0.

In one or more embodiments, the functionalized polymers of thisinvention may be polydienes or copolymers of conjugated diene andco-monomer having medium or low cis-1,4-linkage contents. These polymerscan have a cis-1,4-linkage content of from about 10% to 60%, in otherembodiments from about 15% to 55%, and in other embodiments from about20% to about 50%. These polymers may also have a 1,2-linkage contentfrom about 10% to about 90%, in other embodiments from about 10% toabout 60%, in other embodiments from about 15% to about 50%, and inother embodiments from about 20% to about 45%. In particularembodiments, where the polymers are prepared by employing a functionalanionic initiator, the head of the polymer chain includes a functionalgroup that is the residue of the functional initiator.

In one or more embodiments, the functionalized polymer of this inventionis a polymer selected from the group consisting of polybutadiene,polyisoprene, poly(styrene-co-butadiene),poly(styrene-co-butadiene-co-isoprene), poly(isoprene-co-styrene), andpoly(butadiene-co-isoprene).

In particular embodiments, the functionalized polymers of this inventionare copolymers of 1,3-butadiene, styrene, and optionally isoprene. Thesecopolymer may include random copolymers and block copolymers.

Advantageously, the functionalized polymers of this invention mayprovide rubber compositions that demonstrate reduced hysteresis. Thefunctionalized polymers are particularly useful in preparing rubbercompositions that can be used to manufacture tire components. Rubbercompounding techniques and the additives employed therein are generallydisclosed in The Compounding and Vulcanization of Rubber, in RubberTechnology (^(2nd) Ed. 1973).

The rubber compositions can be prepared by using the functionalizedpolymers alone or together with other elastomers (i.e., polymers thatcan be vulcanized to form compositions possessing rubbery or elastomericproperties). Other elastomers that may be used include natural andsynthetic rubbers. The synthetic rubbers typically derive from thepolymerization of conjugated diene monomers, the copolymerization ofconjugated diene monomers with other monomers such as vinyl-substitutedaromatic monomers, or the copolymerization of ethylene with one or moreα-olefins and optionally one or more diene monomers.

Exemplary elastomers include natural rubber, synthetic polyisoprene,polybutadiene, polyisobutylene-co-isoprene, neoprene,poly(ethylene-co-propylene), poly(styrene-co-butadiene),poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene),poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene),polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber,epichlorohydrin rubber, and mixtures thereof. These elastomers can havea myriad of macromolecular structures including linear, branched, andstar-shaped structures.

The rubber compositions may include fillers such as inorganic andorganic fillers. Examples of organic fillers include carbon black andstarch. Examples of inorganic fillers include silica, aluminumhydroxide, magnesium hydroxide, mica, talc (hydrated magnesiumsilicate), and clays (hydrated aluminum silicates). Carbon blacks andsilicas are the most common fillers used in manufacturing tires. Incertain embodiments, a mixture of different fillers may beadvantageously employed.

In one or more embodiments, carbon blacks include furnace blacks,channel blacks, and lamp blacks. More specific examples of carbon blacksinclude super abrasion furnace blacks, intermediate super abrasionfurnace blacks, high abrasion furnace blacks, fast extrusion furnaceblacks, fine furnace blacks, semi-reinforcing furnace blacks, mediumprocessing channel blacks, hard processing channel blacks, conductingchannel blacks, and acetylene blacks.

In particular embodiments, the carbon blacks may have a surface area(EMSA) of at least 20 m²/g and in other embodiments at least 35 m²/g;surface area values can be determined by ASTM D-1765 using thecetyltrimethylammonium bromide (CTAB) technique. The carbon blacks maybe in a pelletized form or an unpelletized flocculent form. Thepreferred form of carbon black may depend upon the type of mixingequipment used to mix the rubber compound.

The amount of carbon black employed in the rubber compositions can be upto about 50 parts by weight per 100 parts by weight of rubber (phr),with about 5 to about 40 phr being typical.

Some commercially available silicas which may be used include Hi-Sil™215, Hi-Sil™ 233, and Hi-Sil™190 (PPG Industries, Inc.; Pittsburgh,Pa.). Other suppliers of commercially available silica include GraceDavison (Baltimore, Md.), Degussa Corp. (Parsippany, N.J.), RhodiaSilica Systems (Cranbury, N.J.), and J.M. Huber Corp. (Edison, N.J.).

In one or more embodiments, silicas may be characterized by theirsurface areas, which give a measure of their reinforcing character. TheBrunauer, Emmet and Teller (“BET”) method (described in J. Am. Chem.Soc., vol. 60, p. 309 et seq.) is a recognized method for determiningthe surface area. The BET surface area of silica is generally less than450 m²/g. Useful ranges of surface area include from about 32 to about400 m²/g, about 100 to about 250 m²/g, and about 150 to about 220 m²/g.

The pH's of the silicas are generally from about 5 to about 7 orslightly over 7, or in other embodiments from about 5.5 to about 6.8.

In one or more embodiments, where silica is employed as a filler (aloneor in combination with other fillers), a coupling agent and/or ashielding agent may be added to the rubber compositions during mixing inorder to enhance the interaction of silica with the elastomers. Usefulcoupling agents and shielding agents are disclosed in U.S. Pat. Nos.3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919,5,583,245, 5,663,396, 5,674,932, 5,684,171, 5,684,172 5,696,197,6,608,145, 6,667,362, 6,579,949, 6,590,017, 6,525,118, 6,342,552, and6,683,135, which are incorporated herein by reference.

The amount of silica employed in the rubber compositions can be fromabout 1 to about 100 phr or in other embodiments from about 5 to about80 phr. The useful upper range is limited by the high viscosity impartedby silicas. When silica is used together with carbon black, the amountof silica can be decreased to as low as about 1 phr; as the amount ofsilica is decreased, lesser amounts of coupling agents and shieldingagents can be employed. Generally, the amounts of coupling agents andshielding agents range from about 4% to about 20% based on the weight ofsilica used.

A multitude of rubber curing agents (also called vulcanizing agents) maybe employed, including sulfur or peroxide-based curing systems. Curingagents are described in Kirk-Othmer, ENCYCLOPEDIA OF CHEMICALTECHNOLOGY, Vol. 20, pgs. 365-468, (3^(rd) Ed. 1982), particularlyVulcanization Agents and Auxiliary Materials, pgs. 390-402, and A. Y.Coran, Vulcanization, ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING,(2^(nd) Ed. 1989), which are incorporated herein by reference.Vulcanizing agents may be used alone or in combination.

Other ingredients that are typically employed in rubber compounding mayalso be added to the rubber compositions. These include accelerators,accelerator activators, oils, plasticizer, waxes, scorch inhibitingagents, processing aids, zinc oxide, tackifying resins, reinforcingresins, fatty acids such as stearic acid, peptizers, and antidegradantssuch as antioxidants and antiozonants. In particular embodiments, theoils that are employed include those conventionally used as extenderoils, which are described above.

All ingredients of the rubber compositions can be mixed with standardmixing equipment such as Banbury or Brabender mixers, extruders,kneaders, and two-rolled mills. In one or more embodiments, theingredients are mixed in two or more stages. In the first stage (oftenreferred to as the masterbatch mixing stage), a so-called masterbatch,which typically includes the rubber component and filler, is prepared.To prevent premature vulcanization (also known as scorch), themasterbatch may exclude vulcanizing agents. The masterbatch may be mixedat a starting temperature of from about 25° C. to about 125° C. with adischarge temperature of about 135° C. to about 180° C. Once themasterbatch is prepared, the vulcanizing agents may be introduced andmixed into the masterbatch in a final mixing stage, which is typicallyconducted at relatively low temperatures so as to reduce the chances ofpremature vulcanization. Optionally, additional mixing stages, sometimescalled remills, can be employed between the masterbatch mixing stage andthe final mixing stage. One or more remill stages are often employedwhere the rubber composition includes silica as the filler. Variousingredients including the functionalized polymers of this invention canbe added during these remills.

The mixing procedures and conditions particularly applicable tosilica-filled tire formulations are described in U.S. Pat. Nos.5,227,425, 5,719,207, and 5,717,022, as well as European Patent No.890,606, all of which are incorporated herein by reference. In oneembodiment, the initial masterbatch is prepared by including thefunctionalized polymer of this invention and silica in the substantialabsence of coupling agents and shielding agents.

The rubber compositions prepared from the functionalized polymers ofthis invention are particularly useful for forming tire components suchas treads, subtreads, sidewalls, body ply skims, bead filler, and thelike. Preferably, the functional polymers of this invention are employedin tread and sidewall formulations. In one or more embodiments, thesetread or sidewall formulations may include from about 10% to about 100%by weight, in other embodiments from about 35% to about 90% by weight,and in other embodiments from about 50% to about 80% by weight of thefunctionalized polymer based on the total weight of the rubber withinthe formulation.

Where the rubber compositions are employed in the manufacture of tires,these compositions can be processed into tire components according toordinary tire manufacturing techniques including standard rubbershaping, molding and curing techniques. Typically, vulcanization iseffected by heating the vulcanizable composition in a mold; e.g., it maybe heated to about 140° C. to about 180° C. Cured or crosslinked rubbercompositions may be referred to as vulcanizates, which generally containthree-dimensional polymeric networks that are thermoset. The otheringredients, such as fillers and processing aids, may be evenlydispersed throughout the crosslinked network. Pneumatic tires can bemade as discussed in U.S. Pat. Nos. 5,866,171, 5,876,527, 5,931,211, and5,971,046, which are incorporated herein by reference.

In order to demonstrate the practice of the present invention, thefollowing examples have been prepared and tested. The examples shouldnot, however, be viewed as limiting the scope of the invention. Theclaims will serve to define the invention.

Example 1 Synthesis of 4-[Bis(trimethylsilyl)aminomethyl]benzonitrile(4-BTMSAMBZN)

About 5.20 g of 4-(aminomethyl)benzonitrile hydrochloride, 10.30 g oftriethylamine, and 10 ml of toluene were mixed in a round-bottomreaction flask cooled with an ice bath. To this mixture was added, in adropwise fashion, a solution of 15.1 g of trimethylsilyltrifluoromethanesulfonate in 50 ml of toluene. The resulting mixture wasstirred at room temperature for 3 days to give a biphasic mixture. Thetop layer was transferred to another flask, and the bottom layer wasextracted with 40 ml of toluene. The combined toluene solution wasevaporated under vacuum. The residue was extracted with 100 ml ofhexane, and the hexane layer was evaporated under vacuum, yielding4-[bis(trimethylsilyl)aminomethyl]benzonitrile (4-BTMSAMBZN) as a whitesolid (8.12 g, 95% yield). The ¹H NMR data (C₆D₆, 25° C., referenced totetramethylsilane) of the product are listed as follows: δ 7.00(doublet, 2H, aromatic protons), 6.83 (doublet, 2H, aromatic protons),3.72 (singlet, 2H, CH₂ protons), −0.06 (singlet, 18H, Si—CH₃ protons).From the ¹H NMR data, the structure of the product was determined to beas follows:

Example 2 Synthesis of5-[Bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN)

About 6.17 g of 5-amino-2-pyridinecarbonitrile, 11.54 g oftriethylamine, and 10 ml of toluene were mixed in a round-bottomreaction flask cooled with an ice bath. To this mixture was added, in adropwise fashion, a solution of 25.34 g of trimethylsilyltrifluoromethanesulfonate in 70 ml of toluene. The resulting mixture washeated to reflux for 2.5 hours and then evaporated under vacuum. Theresidue was extracted with 100 ml of hexane. The hexane layer was washedtwice with saturated aqueous sodium bicarbonate solution (80 ml eachtime), dried with anhydrous sodium sulfate, and evaporated under vacuum,yielding 5-[bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN)as a green oil (8.67 g, 64% yield). The ¹H NMR data (C₆D₆, 25° C.,referenced to tetramethylsilane) of the product are listed as follows: δ8.07 (doublet of doubets, 1H, aromatic proton), 6.70 (doublet ofdoublets, 1H, aromatic proton), 6.45 (doublet of doublets, 1H, aromaticproton), −0.16 (singlet, 18H, Si—CH₃ protons). From the ¹H NMR data, thestructure of the product was determined to be as follows:

Example 3 Synthesis of 3-[Bis(trimethylsilyl)amino]propionitrile(3-BTMSAPN)

About 5.04 g of 3-aminopropionitrile, 16.01 g of triethylamine, and 10ml of toluene were mixed in a round-bottom reaction flask cooled with anice bath. To this mixture was added, in a dropwise fashion, a solutionof 35.16 g of trimethylsilyl trifluoromethanesulfonate in 50 ml oftoluene. The resulting mixture was stirred at room temperature for 2days to give a biphasic mixture. The top layer was transferred toanother flask, and the bottom layer was extracted with 50 ml of toluene.The combined toluene solution was evaporated under vacuum. The residuewas extracted with 100 ml of hexane, and the hexane layer was evaporatedunder vacuum, yielding 3-[bis(trimethylsilyl)amino]propionitrile(3-BTMSAPN) as a white solid (13.86 g, 90% yield). The ¹H NMR data(C₆D₆, 25° C., referenced to tetramethylsilane) of the product arelisted as follows: δ 2.65 (triplet, 2H, CH₂ protons), 1.59 (triplet, 2H,CH₂ protons), −0.05 (singlet, 18H, Si—CH₃ protons). From the ¹H NMRdata, the structure of the product was determined to be as follows:

Example 4 Synthesis of 3-[(Trimethylsilyl)(methyl)amino]propionitrile(3-TMSMAPN)

To a cold solution of 3-(methylamino)propionitrile (23.4 ml) indichloromethane (350 ml) were added triethylamine (38.3 ml) andtrimethylsilyl chloride (33.2 ml). The mixture was stirred at roomtemperature for 18 hours. The triethylamine hydrochloride salt formedwas filtered off and washed with 40 ml of hexane. The combined filtratewas evaporated by using a rotary evaporator. The residual syrup wasdistilled under vacuum to give3-[(trimethylsilyl)(methyl)amino]propionitrile (3-TMSMAPN) as a yellowliquid. The ¹H NMR data (CDCl₃, 25° C., referenced to tetramethylsilane)of the product are listed as follows: δ 3.07 (triplet, 2H, N—CH₂protons), 2.48 (singlet, 3H, N—CH₃ protons), 2.42 (triplet, 2H, CH₂CNprotons), 0.09 (singlet, 9H, Si—CH₃ protons). From the ¹H NMR data, thestructure of the product was determined to be as follows:

Example 5 Synthesis of N-Trimethylsilyl-3,3′-Iminodipropionitrile(TMSIDPN)

To a cold solution of 3,3′-iminodipropionitrile (24.2 ml) indichloromethane (350 ml) were added triethylamine (30.7 ml) andtrimethylsilyl chloride (26.6 ml). The mixture was stirred at roomtemperature for 18 hours. The triethylamine hydrochloride salt formedwas filtered off and washed with 40 ml of hexane. The combined filtratewas evaporated by using a rotary evaporator. The residual syrup wasdistilled under vacuum to giveN-trimethylsilyl-3,3′-iminodipropionitrile (TMSIDPN) as a pale-yellowliquid. The ¹H NMR data (CDCl₃, 25° C., referenced to tetramethylsilane)of the product are listed as follows: δ 3.15 (triplet, 4H, N—CH₂protons), 2.42 (triplet, 4H, N—CH₂ protons), 0.15 (singlet, 9H, Si—CH₃protons). From the ¹H NMR data, the structure of the product wasdetermined to be as follows:

Example 6 Synthesis of 3-[Bis(trimethylsilyl)amino]benzonitrile(3-BTMSABZN)

About 5.87 g of 3-aminobenzonitrile, 11.57 g of triethylamine, and 10 mlof toluene were mixed in a round-bottom reaction flask cooled with anice bath. To this mixture was added, in a dropwise fashion, a solutionof 25.41 g of trimethylsilyl trifluoromethanesulfonate in 50 ml oftoluene. The resulting mixture was heated to reflux for 12 hours to givea biphasic mixture. The top layer was transferred to another flask, andthe bottom layer was extracted with 40 ml of toluene. The combinedtoluene solution was evaporated under vacuum. The residue was extractedwith 100 ml of hexane, and the hexane layer was evaporated under vacuum,yielding 3-[bis(trimethylsilyl)amino]benzonitrile (3-BTMSABZN) as abrown oil (12.62 g, 97% yield). The ¹H NMR data (C₆D₆, 25° C.,referenced to tetramethylsilane) of the product are listed as follows: δ7.00 (multiplet, 1H, aromatic proton), 6.81 (multiplet, 1H, aromaticproton), 6.67 (multiplet, 1H, aromatic proton), 6.59 (multiplet, 1H,aromatic proton), −0.10 (singlet, 18H, Si—CH₃ protons). From the ¹H NMRdata, the structure of the product was determined to be as follows:

Example 7 Synthesis of 4-[Bis(trimethylsilyl)amino]benzonitrile(4-BTMSABZN)

About 5.09 g of 4-aminobenzonitrile, 10.03 g of triethylamine, and 10 mlof toluene were mixed in a round-bottom reaction flask cooled with anice bath. To this mixture was added, in a dropwise fashion, a solutionof 22.02 g of trimethylsilyl trifluoromethanesulfonate in 50 ml oftoluene. The resulting mixture was heated to reflux for 40 hours to givea biphasic mixture. The top layer was transferred to another flask, andthe bottom layer was extracted with 40 ml of toluene. The combinedtoluene solution was evaporated under vacuum. The residue was extractedwith 100 ml of hexane, and the hexane layer was evaporated under vacuum,yielding 4-[bis(trimethylsilyl)amino]benzonitrile (4-BTMSABZN) as abrown oil (10.77 g, 95% yield). The ¹H NMR data (C₆D₆, 25° C.,referenced to tetramethylsilane) of the product are listed as follows: δ6.93 (doublet, 2H, aromatic protons), 6.43 (doublet, 2H, aromaticprotons), −0.07 (singlet, 18H, Si—CH₃ protons). From the ¹H NMR data,the structure of the product was determined to be as follows:

Example 8 Synthesis of Unmodified Poly(styrene-co-butadiene)

To a 5-gallon nitrogen-purged reactor equipped with turbine agitatorblades were added 5100 g of hexane, 1278 g of 33.0 wt % styrene inhexane, and 7670 g of 22.0 wt % 1,3-butadiene in hexane. To the reactorwere charged 11.98 ml of 1.6 M n-butyllithium in hexane and 3.95 ml of1.6 M 2,2-bis(2′-tetrahydrofuryl)propane in hexane. The batch was heatedby applying hot water to the reactor jacket. Once the batch temperaturereached 50° C., the reactor jacket was cooled with cold water.

Ninety minutes after the addition of the catalyst, about 420 g of theresulting living polymer cement was transferred from the reactor into anitrogen-purged bottle and quenched by addition of 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol. The resultingmixture was coagulated with 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol and then drum-dried.

The Mooney viscosity (ML₁₊₄) of the resulting polymer was determined tobe 13.6 at 100° C. by using a Alpha Technologies Mooney viscometer witha large rotor, a one-minute warm-up time, and a four-minute runningtime. As determined by gel permeation chromatography (GPC), the polymerhad a number average molecular weight (M_(n)) of 116,600, a weightaverage molecular weight (M_(w)) of 120,200, and a molecular weightdistribution (M_(w)/M_(n)) of 1.03. The ¹H NMR analysis of the polymerindicated that the polymer had a styrene content of 21.0 wt % and a1,2-linkage (butadiene mer unit) of 55.5%. The properties of theresulting unmodified poly(styrene-co-butadiene) are summarized in Table1.

TABLE 1 Physical Properties of Poly(styrene-co-butadiene) Example No.Example Example Example Example Example Example Example Example 15Example 16 8 9 10 11 12 13 14 (Comparative) (Comparative) Polymerunmodified unmodified 4- BTMSAPyCN- 3- 3- TMSIDPN- 3- 4- type BTMSAMBZN-modified BTMSAPN- TMSMAPN- modified BTMSABZN- BTMSABZA- modifiedmodified modified modified modified ML₁₊₄ 13.6 97.2 20.7 17.3 19.3 22.343.3 23.5 19.9 at 100° C. M_(n) 116,600 257,500 125,200 116,300 108,600118,200 142,900 133,900 126,600 M_(w) 120,200 282,100 142,200 134,000121,300 133,800 177,000 156,600 144,700 M_(w)/M_(n) 1.03 1.10 1.14 1.151.17 1.13 1.24 1.17 1.14 % 20.7 20.0 20.7 20.7 20.7 20.7 20.7 20.7 20.7styrene % 1,2 55.5 55.9 55.5 55.5 55.5 55.5 55.5 55.5 55.5

Example 9 Synthesis of Unmodified Poly(styrene-co-butadiene)

To a 2-gallon nitrogen-purged reactor equipped with turbine agitatorblades was added 1595 g of hexane, 400 g of 34.0 wt % styrene in hexane,and 2440 g of 22.3 wt % 1,3-butadiene in hexane. To the reactor wascharged 1.70 ml of 1.6 M n-butyllithium in hexane and 0.56 mL of 1.6 M2,2-bis(2′-tetrahydrofuryl)propane in hexane. The batch was heated byapplying hot water to the reactor jacket. Once the batch temperaturereached 50° C., the reactor jacket was cooled with cold water. About 2.5hours after the addition of the catalyst, the polymerization mixture wasquenched with 30 ml of 12 wt % 2,6-di-tert-butyl-4-methylphenol solutionin isopropanol, coagulated with 12 liters of isopropanol containing 5 gof 2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The propertiesof the resulting unmodified SBR are summarized in Table 1.

Example 10 Synthesis of Poly(styrene-co-butadiene) Modified with4-[Bis(trimethylsilyl)aminomethyl]benzonitrile (4-BTMSAMBZN)

About 335 g of the living polymer cement as synthesized in Example 8 wastransferred from the reactor to a nitrogen-purged bottle, followed byaddition of 1.80 ml of 0.237 M4-[bis(trimethylsilyl)aminomethyl]benzonitrile (4-BTMSAMBZN) in hexane.The bottle was tumbled for 30 minutes in a water bath maintained at 65°C. The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 4-BTMSAMBZN-modified polymer are summarized in Table 1.

Example 11 Synthesis of Poly(styrene-co-butadiene) Modified with5-[Bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN)

About 409 g of the living polymer cement as synthesized in Example 8 wastransferred from the reactor to a nitrogen-purged bottle, followed byaddition of 2.22 ml of 0.230 M5-[bis(trimethylsilyl)amino]-2-pyridinecarbonitrile (BTMSAPyCN) inhexane. The bottle was tumbled for 30 minutes in a water bath maintainedat 65° C. The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting BTMSAPyCN-modified polymer are summarized in Table 1.

Example 12 Synthesis of Poly(styrene-co-butadiene) Modified with3-[Bis(Trimethylsilylamino]propionitrile (3-BTMSAPN)

About 429 g of the living polymer cement as synthesized in Example 8 wastransferred from the reactor to a nitrogen-purged bottle, followed byaddition of 2.68 ml of 0.200 M 3-[bis(trimethylsilylamino]propionitrile(3-BTMSAPN) in toluene. The bottle was tumbled for 30 minutes in a waterbath maintained at 65° C. The resulting polymer cement was quenched with3 ml of 12 wt % 2,6-di-tert-butyl-4-methylphenol solution inisopropanol, coagulated with 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 3-TMSMAPN-modified polymer are summarized in Table 1.

Example 13 Synthesis of Poly(styrene-co-butadiene) Modified with3-[(Trimethylsilyl)(methyl)amino]propionitrile (3-TMSMAPN)

About 331 g of the living polymer cement as synthesized in Example 8 wastransferred from the reactor to a nitrogen-purged bottle, followed byaddition of 1.24 ml of 0.335 M3-[(trimethylsilyl)(methyl)amino]propionitrile (3-TMSMAPN) in toluene.The bottle was tumbled for 30 minutes in a water bath maintained at 65°C. The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 3-TMSMAPN-modified polymer are summarized in Table 1.

Example 14 Synthesis of Poly(styrene-co-butadiene) Modified withN-Trimethylsilyl-3,3′-Iminodipropionitrile (TMSIDPN)

About 337 g of the living polymer cement as synthesized in Example 8 wastransferred from the reactor to a nitrogen-purged bottle, followed byaddition of 1.17 ml of 0.361 MN-trimethylsilyl-3,3′-iminodipropionitrile (TMSIDPN) in toluene. Thebottle was tumbled for 30 minutes in a water bath maintained at 65° C.The resulting polymer cement was quenched with 3 ml of 12 wt %2,6-di-tert-butyl-4-methylphenol solution in isopropanol, coagulatedwith 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting TMSIDPN-modified polymer are summarized in Table 1.

Example 15 (Comparative Example) Synthesis of Poly(styrene-co-butadiene)Modified with 3-[Bis(trimethylsilyl)amino]benzonitrile (3-BTMSABZN)

About 344 g of the living polymer cement as synthesized in Example 8 wastransferred from the reactor to a nitrogen-purged bottle, followed byaddition of 1.32 ml of 0.326 M 3-[bis(trimethylsilyl)amino]benzonitrile(3-BTMSABZN) in hexane. The bottle was tumbled for 30 minutes in a waterbath maintained at 65° C. The resulting polymer cement was quenched with3 ml of 12 wt % 2,6-di-tert-butyl-4-methylphenol solution inisopropanol, coagulated with 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 3-BTMSABZN-modified polymer are summarized in Table 1.

Example 16 (Comparative Example) Synthesis of Poly(styrene-co-butadiene)Modified with 4-[Bis(trimethylsilyl)amino]benzonitrile (4-BTMSABZN)

About 334 g of the living polymer cement as synthesized in Example 8 wastransferred from the reactor to a nitrogen-purged bottle, followed byaddition of 1.27 ml of 0.328 M 4-[bis(trimethylsilyl)amino]benzonitrile(4-BTMSABZN) in hexane. The bottle was tumbled for 30 minutes in a waterbath maintained at 65° C. The resulting polymer cement was quenched with3 ml of 12 wt % 2,6-di-tert-butyl-4-methylphenol solution inisopropanol, coagulated with 2 liters of isopropanol containing 0.5 g of2,6-di-tert-butyl-4-methylphenol, and then drum-dried. The properties ofthe resulting 4-BTMSABZN-modified polymer are summarized in Table 1.

Examples 17-25 Compounding Evaluation

The poly(styrene-co-butadiene) samples produced in Examples 8-16 wereevaluated in a rubber compound filled with carbon black. Thecompositions of the vulcanizates are presented in Table 2, wherein thenumbers are expressed as parts by weight per hundred parts by weight oftotal rubber (phr).

TABLE 2 Compositions of Rubber Vulcanizates Prepared fromPoly(styrene-co-butadiene) Ingredient Amount (phr) SBR sample 100 Carbonblack 50 Oil 10 Wax 2 Antioxidant 0.95 Zinc oxide 2.5 Stearic acid 2Accelerators 1.3 Sulfur 1.5 Total 170.25

The Mooney viscosity (ML₁₊₄) of the uncured rubber compound wasdetermined at 130° C. by using a Alpha Technologies Mooney viscometerwith a large rotor, a one-minute warm-up time, and a four-minute runningtime. The Payne effect data (ΔG′) and hysteresis data (tan δ) of thevulcanizates were obtained from a dynamic strain-sweep experiment, whichwas conducted at 60° C. and 10 Hz with strain sweeping from 0.25% to15%. ΔG′ is the difference between G′ at 0.25% strain and G′ at 15%strain. The physical properties of the vulcanizates are summarized inTable 3. In FIG. 1, the tan δ data are plotted against the compoundMooney viscosities.

TABLE 3 Physical Properties of Rubber Vulcanizates Prepared fromPoly(styrene-co-butadiene) Example No. Example Example Example ExampleExample Example Example Example 24 Example 25 17 18 19 20 21 22 23(Comparative) (Comparative) Polymer Example 8 Example 9 Example 10Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 usedPolymer un- un- 4- BTMSAPyCN- 3- 3- TMSIDPN- 3- 4- type modifiedmodified BTMSAMBZN- modified BTMSAPN- TMSMAPN- modified BTMSABZN-BTMSABZN- modified modified modified modified modified Compound 21.486.0 40.6 34.0 28.2 28.9 37.8 34.2 30.3 ML₁₊₄ at 130° C. tanδ at 0.2410.144 0.108 0.118 0.147 0.153 0.119 0.132 0.144 60° C., 5% strain ΔG′(MPa) 4.16 1.71 0.45 0.51 1.04 1.05 0.56 0.69 0.91

As can be seen in Table 3 and FIG. 1, the 4-BTMSAMBZN-, BTMSAPyCN-,3-BTMSAPN-, 3-TMSMAPN-, TMSIDPN-, 3-BTMSABZN-, and 4-BTMSABZN-modifiedpoly(styrene-co-butadiene) samples give lower tan δ than the unmodifiedpolymer, indicating that the modification of poly(styrene-co-butadiene)with 4-BTMSAMBZN, BTMSAPyCN, 3-BTMSAPN, 3-TMSMAPN, TMSIDPN, 3-BTMSABZN,and 4-BTMSABZN reduces hysteresis. The modifiedpoly(styrene-co-butadiene) samples also give significantly lower ΔG′than the unmodified polymer, indicating that the Payne Effect has beenreduced due to the interaction between the modified polymer and carbonblack. In addition, although 4-BTMSAMBZN, BTMSAPyCN, 3-BTMSABZN, and4-BTMSABZN contain the same bis(trimethylsilyl)amino group, thepoly(styrene-co-butadiene) samples (Examples 10, 11, 19, and 20)modified with 4-BTMSAMBZN or BTMSAPyCN where thebis(trimethylsilyl)amino group is directly attached to an acyclic moietyor a heterocyclic moiety provide lower tan δ and lower ΔG′ as comparedto the poly(styrene-co-butadiene) samples (Examples 15, 16, 24, and 25(comparative)) modified with 3-BTMSABZN or 4-BTMSABZN where thebis(trimethylsilyl)amino group is directly attached to an aromaticmoiety that is devoid of heteroatoms.

Various modifications and alterations that do not depart from the scopeand spirit of this invention will become apparent to those skilled inthe art. This invention is not to be duly limited to the illustrativeembodiments set forth herein.

1. A method for preparing a functionalized polymer, the methodcomprising the steps of: (i) polymerizing monomer with an anionicinitiator to form a reactive polymer; and (ii) reacting the reactivepolymer with a nitrile compound containing a protected amino group,where the protected amino group is directly attached to a moietyselected from the group consisting of acyclic moieties, heterocyclicmoieties, and non-aromatic cyclic moieties.
 2. The method of claim 1,where the protected amino group is selected from the group consisting ofbis(trihydrocarbylsilyl)amino, bis(dihydrocarbylhydrosilyl)amino,1-aza-disila-1-cyclohydrocarbyl,(trihydrocarbylsilyl)(hydrocarbyl)amino,(dihydrocarbylhydrosilyl)(hydrocarbyl)amino,1-aza-2-sila-1-cyclohydrocarbyl, dihydrocarbylamino, and1-aza-1-cyclohydrocarbyl groups.
 3. The method of claim 1, where thenitrile compound containing a protected amino group derives from anitrile compound selected from the group consisting of arenecarbonitrilecompounds, alkanecarbonitrile compounds, alkenecarbonitrile compounds,alkynecarbonitrile compounds, cycloalkanecarbonitrile compounds,cycloalkenecarbonitrile compounds, cycloalkynecarbonitrile compounds,and heterocyclic nitrile compounds.
 4. The method of claim 1, where theanionic initiator is an organolithium compound and the monomer includesconjugated diene monomer and optionally monomer copolymerizabletherewith.
 5. The method of claim 1, where both the cyano group and theprotected amino group of the nitrile compound containing a protectedamino group are directly attached to a moiety selected from the groupconsisting of acyclic moieties, heterocyclic moieties, and non-aromaticcyclic moieties.
 6. The method of claim 1, where the nitrile compoundcontaining a protected amino group is an arenecarbonitrile compoundcontaining a protected amino group selected from the group consisting of[bis(trihydrocarbylsilyl)amino]arenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]arenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)arenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]arenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]arenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)arenecarbonitrile,(dihydrocarbylamino)arenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)arenecarbonitrile.
 7. The method of claim 1,where the nitrile compound containing a protected amino group is analkanecarbonitrile compound containing a protected amino group selectedfrom the group consisting of[bis(trihydrocarbylsilyl)amino]alkanecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkanecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkanecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkanecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkanecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkanecarbonitrile,(dihydrocarbylamino)alkanecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkanecarbonitrile.
 8. The method of claim 1,where the nitrile compound containing a protected amino group is analkenecarbonitrile compound containing a protected amino group selectedfrom the group consisting of[bis(trihydrocarbylsilyl)amino]alkenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkenecarbonitrile,(dihydrocarbylamino)alkenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkenecarbonitrile.
 9. The method of claim 1,where the nitrile compound containing a protected amino group is analkynecarbonitrile compound containing a protected amino group selectedfrom the group consisting of[bis(trihydrocarbylsilyl)amino]alkynecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]alkynecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)alkynecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]alkynecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]alkynecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)alkynecarbonitrile,(dihydrocarbylamino)alkynecarbonitrile, and(1-aza-1-cyclohydrocarbyl)alkynecarbonitrile.
 10. The method of claim 1,where the nitrile compound containing a protected amino group is acycloalkanecarbonitrile compound containing a protected amino groupselected from the group consisting of[bis(trihydrocarbylsilyl)amino]cycloalkanecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkanecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkanecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkanecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkanecarbonitrile,(dihydrocarbylamino)cycloalkanecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkanecarbonitrile.
 11. The method ofclaim 1, where the nitrile compound containing a protected amino groupis a cycloalkenecarbonitrile compound containing a protected amino groupselected from the group consisting of[bis(trihydrocarbylsilyl)amino]cycloalkenecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkenecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkenecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkenecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkenecarbonitrile,(dihydrocarbylamino)cycloalkenecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkenecarbonitrile.
 12. The method ofclaim 1, where the nitrile compound containing a protected amino groupis a cycloalkynecarbonitrile compound containing a protected amino groupselected from the group consisting of[bis(trihydrocarbylsilyl)amino]cycloalkynecarbonitrile,[bis(dihydrocarbylhydrosilyl)amino]cycloalkynecarbonitrile,(1-aza-disila-1-cyclohydrocarbyl)cycloalkynecarbonitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]cycloalkynecarbonitrile,(1-aza-2-sila-1-cyclohydrocarbyl)cycloalkynecarbonitrile,(dihydrocarbylamino)cycloalkynecarbonitrile, and(1-aza-1-cyclohydrocarbyl)cycloalkynecarbonitrile.
 13. The method ofclaim 1, where the nitrile compound containing a protected amino groupis a heterocyclic nitrile compound containing a protected amino groupselected from the group consisting of[bis(trihydrocarbylsilyl)amino]heterocyclic nitrile,[bis(dihydrocarbylhydrosilyl)amino]heterocyclic nitrile,(1-aza-disila-1-cyclohydrocarbyl)heterocyclic nitrile,[(trihydrocarbylsilyl)(hydrocarbyl)amino]heterocyclic nitrile,[(dihydrocarbylhydrosilyl)(hydrocarbyl)amino]heterocyclic nitrile,(1-aza-2-sila-1-cyclohydrocarbyl)heterocyclic nitrile,(dihydrocarbylamino)heterocyclic nitrile, and(1-aza-1-cyclohydrocarbyl)heterocyclic nitrile.
 14. A method forpreparing a functionalized polymer, the method comprising the steps of:(i) polymerizing monomer with an anionic initiator to form a reactivepolymer; and (ii) reacting the reactive polymer with a nitrile compoundcontaining a protected amino group defined by the formula I:

where R¹ is a divalent organic group, and R² and R³ are eachindependently a monovalent organic group or a hydrolyzable group, or R²and R³ join to form a divalent organic group, with the proviso that R¹is an acyclic divalent organic group, a heterocyclic divalent organicgroup, a non-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theprotected amino group is not directly attached to the aromatic ring. 15.The method of claim 14, where the nitrile compound containing aprotected amino group is defined by the formula II:

where R¹ and R⁵ are each independently a divalent organic group, and R⁴and R⁶ are each independently a bond or a hydrolyzable group, with theproviso that R¹ is an acyclic divalent organic group, a heterocyclicdivalent organic group, a non-aromatic cyclic divalent organic groupthat is devoid of heteroatoms, or a divalent organic group containing anaromatic ring that is devoid of heteroatoms so long as, where R¹ is adivalent organic group containing an aromatic ring that is devoid ofheteroatoms, the protected amino group is not directly attached to thearomatic ring.
 16. The method of claim 14, where the nitrile compoundcontaining a protected amino group is defined by the formula III:

where R¹ is a divalent organic group, R³ is a monovalent organic groupor a hydrolyzable group, each R⁷ is independently a hydrogen atom or amonovalent organic group, or R³ and one R⁷ join to form a divalentorganic group, with the proviso that R¹ is an acyclic divalent organicgroup, a heterocyclic divalent organic group, a non-aromatic cyclicdivalent organic group that is devoid of heteroatoms, or a divalentorganic group containing an aromatic ring that is devoid of heteroatomsso long as, where R¹ is a divalent organic group containing an aromaticring that is devoid of heteroatoms, the protected amino group is notdirectly attached to the aromatic ring.
 17. The method of claim 16,where the nitrile compound containing a protected amino group is definedby the formula IV:

where R¹ and R⁸ are each independently a divalent organic group, andeach R⁷ is independently a hydrogen atom or a monovalent organic group,with the proviso that R¹ is an acyclic divalent organic group, aheterocyclic divalent organic group, a non-aromatic cyclic divalentorganic group that is devoid of heteroatoms, or a divalent organic groupcontaining an aromatic ring that is devoid of heteroatoms so long as,where R¹ is a divalent organic group containing an aromatic ring that isdevoid of heteroatoms, the protected amino group is not directlyattached to the aromatic ring.
 18. The method of claim 14, where thenitrile compound containing a protected amino group is defined by theformula V:

where R¹ is a divalent organic group, and R⁹ and R¹⁰ are eachindependently a hydrogen atom or a monovalent organic group, or at leastone R⁹ and at least one R¹⁰ join to form a divalent organic group, withthe proviso that R¹ is an acyclic divalent organic group, a heterocyclicdivalent organic group, a non-aromatic cyclic divalent organic groupthat is devoid of heteroatoms, or a divalent organic group containing anaromatic ring that is devoid of heteroatoms so long as, where R¹ is adivalent organic group containing an aromatic ring that is devoid ofheteroatoms, the protected amino group is not directly attached to thearomatic ring.
 19. The method of claim 18, where the nitrile compoundcontaining a protected amino group is defined by the formula VI:

where R¹ and R¹¹ are each independently a divalent organic group, and R⁹and R¹⁰ are each independently a hydrogen atom or a monovalent organicgroup, with the proviso that R¹ is an acyclic divalent organic group, aheterocyclic divalent organic group, a non-aromatic cyclic divalentorganic group that is devoid of heteroatoms, or a divalent organic groupcontaining an aromatic ring that is devoid of heteroatoms so long as,where R¹ is a divalent organic group containing an aromatic ring that isdevoid of heteroatoms, the protected amino group is not directlyattached to the aromatic ring.
 20. The method of claim 14, where theanionic initiator is an organolithium compound and the monomer includesconjugated diene monomer and optionally monomer copolymerizabletherewith.
 21. The method of claim 14, where said step of reactingproduces a reaction product that is subsequently protonated.
 22. Afunctionalized polymer containing a protected amino group, thefunctionalized polymer being defined by the formula VII:

where π is a polymer chain of a polydiene or a copolymer of conjugateddiene and co-monomer having a medium or low cis-1,4-linkage content, R¹is a divalent organic group, and R² and R³ are each independently amonovalent organic group or a hydrolyzable group, or R² and R³ join toform a divalent organic group, with the proviso that R¹ is an acyclicdivalent organic group, a heterocyclic divalent organic group, anon-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theprotected amino group is not directly attached to the aromatic ring. 23.A functionalized polymer containing an amino group, the functionalizedpolymer being defined by the formula VIII:

where π is a polymer chain of a polydiene or a copolymer of conjugateddiene and co-monomer having a medium or low cis-1,4-linkage content, R¹is a divalent organic group, and R¹² and R¹³ are each independently amonovalent organic group or a hydrogen atom, or R¹² and R¹³ join to forma divalent organic group, with the proviso that R¹ is an acyclicdivalent organic group, a heterocyclic divalent organic group, anon-aromatic cyclic divalent organic group that is devoid ofheteroatoms, or a divalent organic group containing an aromatic ringthat is devoid of heteroatoms so long as, where R¹ is a divalent organicgroup containing an aromatic ring that is devoid of heteroatoms, theamino group is not directly attached to the aromatic ring.
 24. A tirecomponent including the vulcanized residue of the functionalized polymerof claim
 22. 25. A tire component including the vulcanized residue ofthe functionalized polymer of claim 23.